CN114318848A - Composite environment-friendly high-flame-retardant filling rope for flame-retardant and fire-resistant cable and preparation method thereof - Google Patents
Composite environment-friendly high-flame-retardant filling rope for flame-retardant and fire-resistant cable and preparation method thereof Download PDFInfo
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- CN114318848A CN114318848A CN202111383838.XA CN202111383838A CN114318848A CN 114318848 A CN114318848 A CN 114318848A CN 202111383838 A CN202111383838 A CN 202111383838A CN 114318848 A CN114318848 A CN 114318848A
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- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a composite environment-friendly high-flame-retardant filling rope for a flame-retardant and fire-resistant cable, which comprises a filling rope base material made of roving made of waste polyester cotton, phosphorus-nitrogen water-based flame-retardant powder is dispersed in the base material, and the outside of the base material is coated with first Mg (OH)2Flame retardant glue layer, said Mg (OH)2A powdery flame-retardant layer is sprayed outside the flame-retardant glue layer, and a second Mg (OH) is coated outside the powdery flame-retardant layer2A flame retardant glue layer, said second Mg (OH)2The outside of the flame-retardant glue layer is coated with a ceramic fire-resistant layer. The invention also discloses a preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable. The invention can make up the defects of poor radiation resistance and no flame-retardant and fire-resistant dual performance of the existing similar products, and has the advantages of excellent flame-retardant and fire-resistant performance, radiation resistance, environmental protection, high cost performance and the like.
Description
Technical Field
The invention relates to a composite environment-friendly high-flame-retardant filling rope for a flame-retardant and fire-resistant cable and a preparation method thereof, belonging to the technical field of cables.
Background
Due to the rapid development of the cable industry, the cable industry has become the second largest industry in the mechanical industry, second only to the automobile industry. The production value of the cable in 2020 has already passed about 15000 trillion yuan, the fire-resistant cable of the flame-retardant cable accounts for about 50% of the cable, the annual demand of the existing flame-retardant fire-resistant cable 2020 reaches nearly 5 trillion yuan, and the annual consumption of the cable core filling rope in the necessary flame-retardant fire-resistant cable reaches more than 5 trillion annual consumption, which still increases by about 10%. At present, the filling ropes used for the flame-retardant and fire-resistant cables in the market are various, and domestic similar products have uneven performances and poor stability and environmental protection. At present, the domestic flame-retardant filling ropes have no flame resistance, and the market of the filling ropes with the flame resistance only has ceramic silicon rubber filling ropes. But has high price, large specific gravity and flame-retardant oxygen index less than 30 percent. Other foreign manufacturers do not have a multi-performance filling material integrating oxidation resistance, long service life, flame retardance and fire resistance, such as flame-retardant and fire-resistant cable core wrapping tapes of products of DuPont and Dongli corporation in Japan, although the performance is superior, the filling material does not have multiple performances of flame retardance, fire resistance, ageing resistance and the like at the same time, and the existing flame-retardant filling ropes are difficult to meet the requirements of long service life, high flame retardance and radiation resistance of cables such as nuclear power cables, high-speed rails and the like running in the world in China. The performance technical indexes of the flame-retardant filling ropes in the existing market are difficult to meet the requirement of high-speed development of high-performance flame-retardant cables.
The flame-retardant filling rope commonly used in the market at present comprises a glass fiber filling rope, a rock wool filling rope, a polypropylene flame-retardant filling rope and other kinds of filling ropes. The current commonly used flame retardant filler rope parameter pairs are as follows:
TABLE 1 Performance parameter Table of existing flame retardant filling rope
As can be seen from the above Table 1, the existing flame-retardant filling rope has the disadvantages of poor radiation resistance and no flame-retardant and fire-resistant dual performance.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention provides the flame-retardant fireproof cable which can make up the defects of poor radiation resistance and no flame-retardant and fireproof dual performance of the existing similar products, and has the advantages of excellent flame-retardant and fireproof performance, radiation resistance, environmental protection, high cost performance and the like.
Meanwhile, the invention provides a preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable, which is characterized in that environment-friendly recycled old polyester clothes and old cotton are adopted to prepare high-temperature-resistant polyester yarns, and then the composite environment-friendly high-flame-retardant filling rope with a multilayer efficient flame-retardant structure is prepared through three-dipping three-bundling and the like.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable comprises a filling rope base material made of roving made of waste polyester cotton, phosphorus-nitrogen water-based flame-retardant powder is dispersed in the base material, and the outside of the base material is coated with first Mg (OH)2Flame retardant glue layer, said Mg (OH)2A powdery flame-retardant layer is sprayed outside the flame-retardant glue layer, and a second Mg (OH) is coated outside the powdery flame-retardant layer2A flame retardant glue layer, said second Mg (OH)2The outside of the flame-retardant glue layer is coated with a ceramic fire-resistant layer.
The waste polyester cotton comprises waste clothes and/or quilts.
The gram weight of the roving is 0.2-0.4g/m, the elongation is more than 15%, and the tensile force is more than 0.5N/10 cm.
The phosphorus-nitrogen water-based flame retardant powder is formed by drying phosphorus-nitrogen flame retardant liquid;
the phosphorus-nitrogen flame retardant liquid comprises the following components in percentage by weight:
nitrogen additive: one or more of urea, guanidine carbonate and melamine formaldehyde: 15% -20%;
phosphorus additive: one or more of tributyl phosphate, caged dicyclic phosphorus and tris (acryloyloxyethyl) phosphate: 15% -20%;
water-based adhesive: 10% -15%;
water: 40% -50%;
the water-based glue comprises pure acrylic glue, vinyl acetate acrylic glue or styrene-acrylic glue.
The first Mg (OH)2A flame retardant glue layer and said second Mg (OH)2The flame-retardant glue layers comprise the following components in percentage by weight: mg (OH)2Powder or Al (OH)3Powder + Mg (OH)2Mixture of powders: 70-80% and VAE emulsion or acrylic emulsion: 20 to 30 percent; the Al (OH)3Powder + Mg (OH)2In the mixture of powders, Al (OH)3The mass percentage of the powder is less than 50 percent; the Al (OH)3Powder and Mg (OH)2The fineness of the powder is 4000-5000 meshes; the VAE emulsion is ethyl acetate copolymer emulsion.
The components of the powdery flame-retardant layer comprise: 4000- & 5000 mesh Al (OH)3Powder or Mg (OH)2And (3) powder.
The ceramic refractory layer comprises the following components in percentage by weight:
30-40% of nanobelt toughened ceramic powder;
10-15% of silica gel;
antimony trioxide: decabromodiphenylethane = 1: 110 to 15 percent;
25 to 30 percent of ethyl acetate
0.05 to 0.1 percent of molybdenum disilicide;
0.05 to 0.1 percent of chromium disilicide;
the coating amount of the ceramic refractory layer is 1-2g/m2。
The preparation method of the nanobelt toughened ceramic powder comprises the following steps: adding 40-50 g/L of aluminum salt aqueous solution, 20-30% of urea aqueous solution, 80-90% of ethanol aqueous solution and ceramic powder into a high-temperature reaction kettle for hydrothermal reaction; the aqueous aluminum salt solution comprises aluminum sulfate and/or aluminum nitrate; the volume ratio of the aluminum salt aqueous solution to the urea aqueous solution to the ethanol aqueous solution is 1: 10: (2-3); the adding weight of the ceramic powder is 100-120 times of that of the aluminum salt aqueous solution; the temperature of the hydrothermal reaction is 120-130 ℃, the time is at least 12 hours, after the reaction is finished, the mixture is centrifuged to obtain a precipitate, and the precipitate is washed, dried and crushed to obtain nanobelt toughened ceramic powder; the nano-belt toughening ceramic powder is Al (OH)3The nanobelt toughens the ceramic powder.
The preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable comprises the following steps:
s01, tearing and crushing waste polyester cotton with different sizes by using a high-speed tearing crusher to generate small blocks, slender block materials and small cotton balls, producing fine fibrous short fibers by using a coarse opener, changing the fine fibrous short fibers into fluffy bodies by using large-bin cotton mixing, collecting by using a fine opener and an air pressure cotton box, carding into nets by using a carding machine, and finally producing 2-3 pieces of roving by air spinning;
s02, immersing the roving in P-N flame-retardant liquid, extruding the roving through P-N flame-retardant liquid to remove excessive water, and feeding into the first Mg (OH)2A flame-retardant glue groove, coating Mg (OH) on the outer part of the roving2The flame-retardant adhesive is extruded by a compression roller, and the surface of the roving is sprayed with dry powder Al (OH)3 Or Mg (OH)2Then enters a second Mg (OH)2The flame-retardant glue groove is extruded by a compression roller and then dried;
s03, the ceramic fire-resistant layer is obtained by dipping ceramic silicon rubber functional liquid, and the preparation method of the ceramic silicon rubber functional liquid comprises the following steps: preparing the nano-belt toughening ceramic powder, silica gel and antimony trioxide according to the proportion: decabromodiphenylethane = 1: 1. adding ethyl acetate, molybdenum disilicide and chromium disilicide into a stirrer, stirring for at least 24 hours at a stirring speed of 400-600 revolutions per minute, and uniformly stirring to obtain a ceramic silicon rubber functional liquid;
and S04, after drying, roughening the surface, dipping the rough yarn into the ceramic silicon rubber functional liquid, and then carrying out surface blade coating, vacuum drying and rolling to obtain the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable.
The power of the high-speed tearing crusher is more than 50kw, and the rotating speed is at least 80 r/min; the power of the coarse opener is 10 kw; the length of the fine fibrous staple fibers is 0.5-10 mm.
The invention has the following beneficial effects:
aiming at the problems that the cable core filling rope special for the flame-retardant cable in the current market has poor flame retardance, has dual performances of flame retardance and fire resistance, and is difficult to meet the production process requirements of high-quality flame-retardant cables developed at high speed in the market. Particularly, the flame-retardant filling rope at the present stage hardly meets the requirements of nuclear-grade high-flame-retardant and long-service-life cables, and the novel high-flame-retardant filling rope special for the flame-retardant and flame-retardant cable has high flame-retardant performance and can meet the service life of more than 60 years.
The invention relates to cotton prepared by blending waste polyester-cottonThe yarn is used as the base material of the filling rope, and has good radiation resistance. The fiber manufactured by utilizing the waste regenerated cotton waste utilization technology has high temperature resistance (the melting point is 260 ℃), good elongation (more than 15%), low manufacturing cost and great contribution to the social benefit and environmental protection, and overcomes the defect that glass fiber and rock wool carcinogenic substances harmful to human bodies are used as base materials in the market to manufacture the filling rope without elongation, high water content and roundness. Replaces the filling rope made of polypropylene particle flame-retardant master batch and filling master batch in the market, has more impurities, large content of heavy metal components and a large amount of CaCO (calcium carbonate) as a hygroscopic material3And the prepared filling rope has the defects of poor roundness, hygroscopicity, oxidation corrosion on conductors Al and Cu and the like.
The invention uses the technology of repeatedly dipping and spraying the flame retardant powder to the polyester cotton yarn to form a plurality of flame retardant and fireproof structure layers to improve the flame retardant and fireproof performance. The specific process comprises the following steps: firstly, polyester cotton yarn is soaked in environment-friendly phosphorus-nitrogen flame retardant liquid → then is soaked in composite flame retardant liquid of aluminum hydroxide and magnesium hydroxide → then is sprayed with flame retardant powder → is coated with ceramic silicone rubber functional liquid and the like, so that the multifunctional flame retardant cable has the characteristics of flame retardance, fire resistance, moisture absorption resistance and the like, has the oxygen index of more than 60 percent and excellent fire resistance, overcomes the defects that the flame retardant performance in the current market is poor, and a filling rope with excellent flame retardance and fire resistance is not simultaneously used, and is difficult to meet the manufacturing process of a high-performance flame retardant and fire-resistant cable.
The invention uses the oxidation-resistant layer self-locking structure process, breaks through the performance that the functional composite surface has a mechanical interlocking structure, creatively manufactures the inert oxidation layer on the surface of the functional fiber, overcomes the problem that the thermal expansion coefficients of the functional composite fiber and the surface of a coating are not matched at different temperatures, weakens the tendency of the coating to fall off and crack on the surface of the functional composite fiber, increases the surface inertia, and overcomes the defects that like products in the market have poor radiation resistance and short service life and cannot adapt to the manufacturing requirements of nuclear-grade cables.
And (IV) the surface roughening process is used, so that the surface roughness is improved, the coating amount is increased, and the effects of no powder falling during adsorption and stable performance are achieved. Overcomes the defects of the similar products in the market such as less adsorbed flame-retardant components, low oxygen index, flame retardance of yarns in the market, easy powder falling and the like.
Drawings
FIG. 1 is a flow chart of the preparation method of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. The specific embodiments described herein are merely illustrative of the invention and are not intended to be limiting.
Example 1:
(I) preparation of raw materials
Waste clothes, waste quilts and the like are purchased in the market, and the raw material components comprise terylene chemical fibers, pure cotton, polyester-cotton blended fabrics and a small amount of linen textiles.
(II) Equipment procurement
Firstly, a tearing and crushing shredding machine: qingdao hong Da Spine Co;
the coarse opening and large bin cotton mixing machine comprises: the ever-maturing natural force non-woven fabric equipment company, the Qingdao macro textile Co., Ltd;
③ the carding machine: dichroa virginica textile machinery, ltd, Qingxi Xinhua textile machinery, ltd;
fourthly, the warping machine: four-frame new technology manufacturing company, Jiangyin, and Zhuyang Dongxiang textile machinery company;
sizing machine: sunrise textile machinery, inc, santocheng walt textile machinery, inc;
sixthly, the roughening machine: wuzhou Wujin Guangyu Yuhua roller machinery, Inc., Jiangyin profit machinery, Inc.;
seventhly, winding and wrapping the yarn machine: wuzhou Wujin Guangyu Yuhua roller machinery, Inc., Jiangyin profit machinery, Inc.;
eighthly, a winding machine: kajie machinery, Inc. in Jiangyin city and Wang Ying Intelligent science and technology, Inc. in Dongguan;
ninja oxygen index tester-Nanjing Jiangning Analyzer GmbH;
tube resistance (fire resistance test): yangzhou Diamond mechanical works;
⑪ ROSH detector: suzhou three-valued precision instruments, Inc.;
⑫ tension meter: shanghai Sanshu instruments science and technology, Inc.;
⑬ aging chamber: yangzhou city diamond mechanical factory.
(III) a yarn making process flow: namely, the preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable comprises the following steps:
firstly, waste clothes, cotton material → a 50kw high-power coarse type tearing and smashing filamentation machine (rotating speed 80 r/min) is used for smashing large pieces of material → small pieces of narrow and long cloth pieces and cotton slivers → a 20kw fine type tearing and smashing filamentation machine is used for generating filamentation → a second fine type tearing and smashing machine is used for generating short fiber filamentation → coarse opening is further used for stirring and turning over filamentation → large bin cotton mixing, air throwing fiber dispersion → a cotton carding machine air pressure tank is used for collecting, the fiber is conveyed to a 186F type 1m wide type cotton carding machine under a certain pressure, and a mesh (95-98 cm wide net, 10-20g/m heavy) is produced2) → short fiber is made by spinning 2-3 thick yarns by air spinning.
Secondly, preparing a warping pan head, and uniformly arranging yarns on the pan head (phi 60-80 cm) by using a warping machine with the width of 1 meter and 6 meters according to the process of 3 yarns/cm density.
③ flame-retardant processing flow:
through three-dipping and one-time spraying and drying processes, the prepared flame-retardant yarn has an oxygen index of more than 60 percent, an elongation of more than 15 percent and a diameter of 0.5-1mm per yarn.
(1) Dipping phosphorus-nitrogen P-N aqueous solution, the width of a roving coiled head is 1.6, the diameter is 60-80cm, and a magnetic powder 10kg brake is adopted to achieve a constant speed yarn releasing process. The roving frame is immersed into a sizing tank (the width is 1.8 meters), and the pressure of a compression roller is set to be 2kg (ensuring that the roving contains 50-60% of P-N flame retardant).
(2) The flame-retardant liquid tank is soaked, the pressure of a compression roller is set to be 2kg, the coating increment is guaranteed to reach 30-40%, and the P-N flame-retardant liquid is very easy to absorb moisture after being dried, so that the contact effect of air and the outside is achieved by coating the flame-retardant liquid component (containing acrylic acid or VAE colloid component).
(3) The spraying process, after the step (2), uses an intelligent powder gun to spray powder by utilizing the adhesive property of the surface of the colloid due to the small surface coating amountSpraying powder from top to bottom. The pressure of the spray gun is set to be 2 atmospheric pressures, and the width of the spray nozzle is set to be 1.6-1.8 m. Spraying Mg (OH) onto the upper and lower surfaces of the yarn in the form of mist2Or Al (OH)3The mesh number is 4000-5000 meshes, and the coverage rate of the powder content on the surface reaches 100 percent.
(4) The third dipping and binding process, the surface of the yarn is dipped and bound with a flame-retardant liquid groove again, the pressure of a compression roller is set to be 2kg, the dipping amount is increased by 40 to 50 percent, and because the flame-retardant Mg (OH) is sprayed2Or Al (OH)3The dry powder is dipped and coated again, and after drying, the powder is not removed, and the flame retardant stability is ensured.
(5) The drying process comprises the steps of passing through a sizing machine oven (length is 10-20 m), temperature (100-.
(IV) fire resistance processing flow
Firstly, a surface roughening process, namely after the procedure of preparing and drying the flame-retardant yarn, the prepared flame-retardant coiled yarn → unwinding (adopting a magnetic powder brake of 5-10 kg) → row-dividing steel buttons (3-4 buttons/cm, each button being provided with a hole) → surface roughening rollers (adopting chrome-plated rollers of 200 meshes for upper and lower rollers, wherein the rotating speed is higher than the running speed of the yarn, so that the surface of the flame-retardant yarn has a disordered scratch phenomenon, and the coating adsorption quantity is increased conveniently during dip-coating in the next procedure.
② a fire-resistant dipping coating drying process, the sanded fire-resistant yarn → the yarn passes through row steel buttons (3-4 pieces/cm, each button is provided) → a fire-resistant glue groove (length multiplied by width multiplied by height =2 multiplied by 0.5 meter) → surface coating → dip coating increment of 80-100% → vertical drying → rolling disk head → multi-head rolling machine (adopting 25kg torque motor, 100 rolling heads are provided on each surface of the rolling machine), and 1-4 doubling rolling (selected according to the outer diameter of the rope) is adopted.
a, for a phi 1-6mm specification flame-retardant fire-resistant filling rope: the twisting machine can twist 1 or more yarns into a round shape at one time.
b, stranding process of the flame-retardant and fire-resistant filling rope with the specification of phi 6-9 mm: the twisted yarn is obtained by directly twisting and rolling by adopting a stranding and pair twisting rotary twisting process and a small pair twister with the diameter of 1-1.2 mm.
c for phi 10-20 mm: the natural doubling and external winding yarn binding process is adopted, the winding mode is S-shaped binding, and the yarn binding adopts 150-dtex 250dtex terylene flame-retardant yarn.
Specific dimensions are shown in table 2 below.
TABLE 2 filling rope stranding process table
(VI) packaging
The winding inner hole phi is 50-80mm, a tube core with a required aperture can be selected, and the winding can be selected.
The product performance indicators obtained in this example are set forth in Table 3 below.
Table 3 table of performance parameters of the filler ropes obtained in example 1
Example 2:
as shown in fig. 1, the preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable comprises the following steps:
a, waste and old fabrics and quilts with different sizes are processed by a high-speed tearing and crushing machine (more than 50kw, the rotating speed is 80 r/min, alloy materials are used as the materials of the crushed cutting knife) through the tearing and crushing machine → small blocks, slender block materials and small cotton balls are produced → a 10kw coarse opener (the yield can reach 1000kg/h, the fiber length is 0.5-10 mm) is used (producing finer fibrous short fibers) → a large-bin cotton mixing process (fully dividing the produced fibers into fluffy bodies) → a fine opening process (further opening and opening separation) → pneumatic cotton box collection → an F carding machine carding and netting → air spinning to produce coarse yarns (2-3). The method replaces the prior art that a crusher (the cloth is fragile and easy to be agglomerated)) is used for → a blue and white machine → multi-bin cotton mixing → an air pressure ladder box → a carding machine → drawing → air flow spinning. The production process of the filamentization machine overcomes the defects of low fiber forming speed, poor fiber forming qualification rate, no mixed coexistence state of fiber and fragments, more working procedures and the like. The waste cotton yarn prepared by the embodiment can produce the cheap yarn filling material with 2-3 rove gram weight of 0.2-0.4g/m, the elongation rate of more than 15 percent and the pulling force of more than 0.5N/10cm, and has high efficiency, low production cost and good environmental protection.
(2) Flame-retardant process
Impregnating and phosphorus-nitrogen flame-retardant liquid and coating flame-retardant glue and spraying dry powder Mg (OH) on yarns2The cotton yarn contains multiple layers of flame-retardant components from inside to outside, achieves high flame-retardant oxygen index (more than 60 percent) and non-hygroscopicity, and accords with the ROHS high-quality flame-retardant filling rope, and the specific implementation process is as follows:
firstly, a sizing machine is provided with a plurality of dipping and binding glue grooves, three dipping and binding functions are realized, roving is firstly immersed into phosphorus-nitrogen water-based flame retardant liquid (hereinafter referred to as P-N), so that the flame retardant component P-N is immersed into the inner core part of the yarn, and the defect that the inner part of the yarn has no flame retardant component in the traditional process is overcome (the traditional process is used for dipping and binding creamy flame retardant glue on cotton yarn, and the flame retardant glue component is difficult to permeate into the cotton).
And secondly, after P-N liquid is soaked, excessive moisture is removed through compression roller extrusion, the yarn enters a flame-retardant glue tank, flame-retardant glue is coated on the outer part of the yarn again, and the yarn is extruded through the compression roller.
The phosphorus-nitrogen flame retardant liquid comprises the following components:
nitrogen additive: 5% of urea, 6% of guanidine carbonate and 4% of melamine formaldehyde;
phosphorus additive: tributyl phosphate 4%, caged dicyclophosphorus 8% and tris (acryloyloxyethyl) phosphate 8%;
water-based glue (pure acrylic glue): 15 percent;
water: 50 percent;
flame retardant adhesive composition
Al(OH)3 Mg(OH)2：70%；
VAE emulsion or acrylic emulsion: 30 percent;
Al(OH)3 Mg(OH)2 in (C), Al (OH)3In a percentage of less than 50% or Mg (OH)2The components are 100 percent;
the VAE emulsion is ethyl acetate copolymer emulsion;
Al(OH)3、Mg(OH)2the fineness of the powder is 40The particle size of the powder is larger as the mesh number is smaller, but the flame retardant property is reduced; the larger the mesh number is, the smaller the particle size of the powder is, and the higher the flame retardant property is.
The process has 2 advantages:
a surface is additionally coated with Mg (OH)2A flame-retardant layer is added;
b coating the N-P flame-retardant layer, wherein the P-N component has the defects of easy moisture absorption and moisture regain, and a coating Mg (OH) is used2The P-N component is isolated from air by the flame retardant glue, and the moisture absorption and the moisture regain phenomenon are avoided.
Thirdly, spraying dry powder Al (OH) on the surface of the yarn after the process3Or Mg (OH)2The mesh number is 4000-3Or Mg (OH)2Forming a powdery flame-retardant layer to increase flame retardancy, Al (OH)3And Mg (OH)2The fire retardant is natural mineral powder with halogen-free components, low cost and no toxicity.
And fourthly, after the third procedure, the powder enters a flame-retardant glue groove and is soaked → extruded, so that the surface of the flame-retardant powder layer is coated with the flame-retardant glue solution, the flame-retardant layer is added, and the powder layer is coated to prevent the powder layer from falling off, falling off and flying.
And (6) drying, namely drying in a drying oven (150 ℃) of 10-20 meters to a drying roller after the procedure (IV). And (5) sanding the surface after drying.
Through the processes of soaking, pressing, spraying and drying, the yarn inner core has four efficient flame-retardant layers, and the flame-retardant yarn inner core has stable and durable flame-retardant performance, and overcomes the defects of poor flame retardance of the like products and inflammability after secondary combustion.
The product of the embodiment has high flame retardance (more than 60 percent), no moisture absorption, environmental protection and low manufacturing cost (natural mineral powder Al (OH)3、 Mg(OH)2And the price of the P-N flame retardant is low), and the ideal flame-retardant filling material with high efficiency, environmental protection, low cost and low water content is achieved by using the working principle of a sizing machine and applying a three-dipping three-rolling process.
(3) Refractory performance process
Outer layer coating ceramicThe flame-retardant yarn after the fifth process is subjected to a ceramic silicon rubber dipping functional liquid coating process, and the coating amount reaches 1-2g/m2Then, the surface is subjected to blade coating → vacuum drying → rolling process. Because the ceramic refractory liquid coated outside is encrusted after combustion, the encrusted refractory liquid can resist the temperature of 2000 ℃, and the surface does not crack at the high temperature of 950 ℃ and 4 hours, the flame retardant property (oxygen index is more than 60%) is formed, the fire resistance is excellent, the defects that the existing similar products do not have the double properties of flame retardance and fire resistance are overcome, and the excellent cable core internal filling material is provided for the high-performance flame-retardant and fire-resistant cable.
Proportioning the ceramic silicone rubber: nano-belt toughening ceramic powder: 40 percent;
silica gel: 15 percent;
antimony-based flame retardants (antimony trioxide: decabromodiphenylethane = 1: 1): 15 percent;
ethyl acetate: 29.9 percent;
molybdenum disilicide: 0.05 percent;
chromium disilicide: 0.05 percent;
in the embodiment, silicon, molybdenum and chromium are added into the formula of the refractory colloid to form molybdenum disilicide and chromium disilicide, the molybdenum disilicide and the chromium disilicide have the properties similar to those of metal and ceramic, and can be applied to a high-temperature oxidation-resistant coating material, and a silicon dioxide passivation layer can be formed on the surface at high temperature to prevent further oxidation.
In the embodiment, the oxygen index of the ceramic silicon rubber coating is increased (namely, the flame retardant property is improved) through the antimony flame retardant; the oxidation resistance of the ceramic silicon rubber coating at high temperature is improved through molybdenum disilicide and chromium disilicide, the compactness and the stability of crusting after combustion are improved, and a cable core material in the cable is protected more efficiently.
The embodiment has the following beneficial effects:
the waste is recycled, the manufacturing cost is low, and the social public welfare is good
Firstly, the old cloth, the broken cloth and the waste wadded jacket are recycled.
a has wide material supply: a large amount of waste clothes and cotton products can be recycled;
b, the purchase price is low;
c, the environment is protected, and the social public welfare is good (the waste clothes and cotton products are treated by burning, deep burying and the like in the past);
preparing roving (2-3 yarns) by using a tearing and crushing machine → coarse opening → cotton blending → carding machine → air spinning process, and having the following advantages:
the preparation of the A is simpler than that of the traditional process, and can realize 1000kg/h per hour under the same proportion, which is improved by more than 30 percent than that of the traditional process;
the fiber prepared by the method B has the advantages of long and uniform fiber length and thickness, no hard block and hardened cloth, so that the regenerated yarn has high thickness uniformity and large elongation which is more than 15 percent and is 5 to 10 percent better than similar products.
And C, a closed tearing crusher is used, so that the closed cloth dust fibers and the like have less flying, and the environment is protected.
And (II) multiple processes of dipping and powder spraying coating are applied to achieve a multilayer efficient flame-retardant product, and the oxygen index reaches more than 60%. The phenomena that the oxygen index of the prior similar product is less than 40 percent, the flame retardant stability is poor, the flame retardant powder is easy to remove and the like are overcome.
The phosphorus-nitrogen water-based flame retardant which has high-efficiency flame retardance and low cost for yarn immersion is used, so that the high-efficiency flame-retardant effect in the yarn is achieved, the defects that the similar products have no flame retardance and can be burned again in the yarn after being burned outside at present are overcome, and the flame-retardant property of the product from inside to outside is improved.
② secondary Mg (OH) by utilizing dipping2The flame-retardant liquid and the surface powder spraying process form a plurality of flame-retardant layers, so that the flame-retardant layer has flame retardance (oxygen index is more than 60 percent), has no hygroscopicity, and overcomes the defects that similar products are difficult to use P-N flame retardants, are easy to absorb moisture, have low oxygen index (less than 40 percent) and can be re-combusted after combustion.
A, the process of dipping the phosphorus-nitrogen aqueous liquid flame retardant is used, so that the aqueous liquid phosphorus-nitrogen component permeates into the cotton yarn, and the internal and external flame retardance of the cotton yarn is achieved. The phenomenon of re-burning is not easy to occur, and the phenomenon that the filling ropes of similar products in the market are inconsistent in internal and external flame retardance and easy to re-burn due to burning is overcome.
B using dip-prick flame retardant Mg (OH)2Colloid → spray Mg (OH)2Dry powder → dip-stick flame retardant Mg (OH)2The colloid process has the following advantages:
the flame-retardant fiber has a multi-layer flame-retardant layer structure, the oxygen index is more than 60 percent, and the defects that the single-layer flame-retardant layer structure or the whole flame retardance difference of the existing similar products is lower than 40 percent (the oxygen index of glass fiber and rock wool filling paper is more than 50 percent, the flame-retardant cotton yarn is less than 40 percent, and the polypropylene flame-retardant filling rope is less than 30 percent) are overcome.
Form a plurality of flame retardant layers for isolating air, isolate the phosphorus-nitrogen component from air, avoid moisture absorption and moisture regain, and overcome the difficulty in using cheap and excellent flame retardant P-N flame retardant in the prior similar products.
And (III) the flame-retardant fireproof paint has excellent flame-retardant and fireproof double performances, the ceramic fireproof colloid is soaked to achieve the fireproof performance, the surface does not crack at the high temperature of 950 ℃ for 4h, and the defect that the traditional process does not have the flame-retardant and fireproof double performances is overcome. The material is suitable for filling various high-performance flame-retardant and fire-resistant cables.
And (IV) the surface roughening process is used, so that the adsorption quantity of the surface fire-resistant glue is increased, the adsorption quantity can be increased by 40%, the stability of the fire resistance is improved, and the defects of smoothness, difficulty in adsorption and easiness in powder removal after surface coating in the traditional process are overcome.
The process for preparing the surface oxidation resistant layer comprises the steps of adding silicon, molybdenum and chromium components into a formula of a refractory colloid, mixing to form molybdenum disilicide and chromium disilicide, so that the coated surface has the function of an oxidation resistant layer self-locking structure, the stability of flame retardance and tensile strength of a product in a high-temperature irradiation environment is improved, and the defects of poor irradiation resistance and easy surface oxidation of the conventional like products are overcome. Is an optimal ideal material for filling nuclear-grade cables.
And (VI) naturally stranding the large outer diameter (more than 10 mm) and bundling the strands to form an S-shaped winding technology, so that the winding is fast and the efficiency is high. The filling rope has the advantages of compactness and roundness, light specific gravity and rounded filling effect, and overcomes the defects of labor and time waste and poor efficiency caused by the fact that bundling and pair twisting with different outer diameters are adopted in the traditional process.
The performance indexes of the product in the embodiment are as follows: the oxygen index is more than 60 percent; fire resistance: the surface does not crack at 950 ℃ for 4 h; the water content is less than 1 percent; environmental protection property: no halogen, and meets ROHS standard; no hygroscopicity; the elongation is more than 15 percent.
Example 3
The composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable comprises a filling rope base material made of roving made of waste polyester cotton, phosphorus-nitrogen water-based flame-retardant powder is dispersed in the base material, and the outside of the base material is coated with first Mg (OH)2Flame retardant glue layer, said Mg (OH)2A powdery flame-retardant layer is sprayed outside the flame-retardant glue layer, and a second Mg (OH) is coated outside the powdery flame-retardant layer2A flame retardant glue layer, said second Mg (OH)2The outside of the flame-retardant glue layer is coated with a ceramic fire-resistant layer.
The waste polyester cotton comprises waste clothes and/or quilts.
The gram weight of the roving is 0.2-0.4g/m, the elongation is more than 15%, and the tensile force is more than 0.5N/10 cm.
The phosphorus-nitrogen water-based flame retardant powder is formed by drying phosphorus-nitrogen flame retardant liquid;
the phosphorus-nitrogen flame retardant liquid comprises the following components in percentage by weight:
nitrogen additive: urea: 20 percent;
phosphorus additive: tributyl phosphate: 15 percent;
water-based glue (vinegar acrylic glue): 15 percent;
water: 50 percent.
The first Mg (OH)2A flame retardant glue layer and said second Mg (OH)2The flame-retardant glue layers comprise the following components in percentage by weight: mg (OH)2Powder: 80% and acrylic emulsion: 20 percent; the Al (OH)3The fineness of the powder is 4000 meshes.
The components of the powdery flame-retardant layer comprise: 4000 mesh Mg (OH)2And (3) powder.
The ceramic refractory layer comprises the following components in percentage by weight:
nano-belt toughening ceramic powder: 40 percent;
silica gel: 15 percent;
(antimony trioxide: decabromodiphenylethane = 1: 1): 15 percent;
ethyl acetate: 29.8 percent
Molybdenum disilicide: 0.1 percent;
chromium disilicide: 0.1 percent;
the coating amount of the ceramic refractory layer is 1g/m2。
The preparation method of the nanobelt toughened ceramic powder comprises the following steps: adding 40g/L of aluminum salt aqueous solution, 20% of urea aqueous solution, 80% of ethanol aqueous solution and ceramic powder into a high-temperature reaction kettle for hydrothermal reaction; the aluminum salt aqueous solution is aluminum sulfate; the volume ratio of the aluminum salt aqueous solution to the urea aqueous solution to the ethanol aqueous solution is 1: 10: 2; the adding weight of the ceramic powder is 100 times of that of the aluminum salt aqueous solution; the temperature of the hydrothermal reaction is 120 ℃, the time is 12 hours, after the reaction is finished, the mixture is centrifuged to obtain precipitate, and the precipitate is dried and crushed after being washed to obtain nano-belt toughened ceramic powder; the nano-belt toughening ceramic powder is Al (OH)3The nanobelt toughens the ceramic powder.
The embodiment applies the oxidation-resistant layer self-locking structure process, breaks through the performance that the functional composite surface has a mechanical interlocking structure, innovatively manufactures the functional fiber surface with the inert oxidation layer, overcomes the problem that the thermal expansion coefficients of the functional composite fiber and the surface of the coating are not matched at different temperatures, weakens the tendency of the coating to fall off and crack on the surface of the functional composite fiber, increases the surface inertia, and overcomes the defects that like products in the market have poor irradiation resistance and short service life and cannot adapt to the manufacturing requirements of nuclear-grade cables.
The preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable comprises the following steps:
s01, tearing and crushing waste polyester cotton with different sizes by using a high-speed tearing crusher to generate small blocks, slender block materials and small cotton balls, producing fine fibrous short fibers by using a coarse opener, changing the fine fibrous short fibers into fluffy bodies by using large-bin cotton mixing, collecting by using a fine opener and an air pressure cotton box, carding into nets by using a carding machine, and finally producing 2-3 pieces of roving by air spinning;
s02, immersing the roving in P-N flame-retardant liquid, extruding the roving through P-N flame-retardant liquid to remove excessive water, and feeding into the first Mg (OH)2A flame-retardant rubber groove for the outer side of the rovingPartially coated with Mg (OH)2The flame-retardant adhesive is extruded by a compression roller, and the surface of the roving is sprayed with dry powder Al (OH)3 Or Mg (OH)2Then enters a second Mg (OH)2The flame-retardant glue groove is extruded by a compression roller and then dried;
s03, the ceramic fire-resistant layer is obtained by dipping ceramic silicon rubber functional liquid, and the preparation method of the ceramic silicon rubber functional liquid comprises the following steps: preparing the nano-belt toughening ceramic powder, silica gel and antimony trioxide according to the proportion: decabromodiphenylethane = 1: 1. adding ethyl acetate, molybdenum disilicide and chromium disilicide into a stirrer, stirring for 24 hours at the stirring speed of 400 revolutions per minute, and uniformly stirring to obtain the ceramic silicon rubber functional liquid;
and S04, after drying, roughening the surface, dipping the rough yarn into the ceramic silicon rubber functional liquid, and then carrying out surface blade coating, vacuum drying and rolling to obtain the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable.
The power of the high-speed tearing crusher is 60kw, and the rotating speed is 100 r/min; the power of the coarse opener is 10 kw; the length of the fine fibrous short filaments is about 0.5 mm.
The embodiment has the following beneficial effects:
(1) the method creatively utilizes the technology of rapidly preparing the terylene roving from waste clothes, cotton and the like to prepare the flame-retardant and fire-resistant filling rope base material with excellent cost performance, and simultaneously solves the problem of recycling a large amount of waste clothes, cotton quilts and the like in the market. The terylene base material is high temperature resistant, environment-friendly, free of moisture, good in elongation (more than 15%), good in yarn twist and round in filling, and overcomes the defects that the terylene base material is easy to harm human bodies and has large environmental pollution and the like because glass fibers and rock wool which are good in high temperature resistance and flame retardance are used as materials in the market.
(2) Overcomes the defects of glass fiber and rock wool such as large specific gravity, high water content and unfriendly manufacturing process to the environment, no elongation performance and easy oxidation and corrosion to conductors. Overcomes the defects of low flame-retardant oxygen index, more impurities, non-roundness, easy moisture absorption and the like of the conventional flame-retardant polypropylene filling rope.
The performance indexes of the product in the embodiment are as follows: the oxygen index is more than 60 percent; fire resistance: the surface does not crack at 950 ℃ for 4 h; the water content is less than 1 percent; environmental protection property: no halogen, and meets ROHS standard; no hygroscopicity; the elongation is more than 15 percent.
Example 4
This example differs from example 3 only in that:
the phosphorus-nitrogen flame retardant liquid comprises the following components in percentage by weight:
nitrogen additive: guanidine carbonate: 20 percent;
phosphorus additive: 10% of caged dicyclic phosphorus and 10% of tris (acryloyloxyethyl) phosphate;
water-based glue (styrene-acrylic glue): 10 percent;
water: 50 percent.
The first Mg (OH)2A flame retardant glue layer and said second Mg (OH)2The flame-retardant glue layers comprise the following components in percentage by weight: al (OH)3Powder + Mg (OH)2Mixture of powders: 75% and VAE emulsion: 25 percent; the Al (OH)3Powder + Mg (OH)2In the mixture of powders, Al (OH)3The mass percentage of the powder is 40 percent; the Al (OH)3Powder and Mg (OH)2The fineness of the powder is 5000 meshes; the VAE emulsion is ethyl acetate copolymer emulsion.
The components of the powdery flame-retardant layer comprise: 5000 mesh Al (OH)3And (3) powder.
The coating amount of the ceramic refractory layer is 2g/m2。
The preparation method of the nanobelt toughened ceramic powder comprises the following steps: adding 50g/L of aluminum salt aqueous solution, 30% of urea aqueous solution, 90% of ethanol aqueous solution and ceramic powder into a high-temperature reaction kettle for hydrothermal reaction; the aluminum salt aqueous solution is aluminum nitrate; the volume ratio of the aluminum salt aqueous solution to the urea aqueous solution to the ethanol aqueous solution is 1: 10: 3; the adding weight of the ceramic powder is 120 times of that of the aluminum salt aqueous solution; the temperature of the hydrothermal reaction is 130 ℃, the time is 18h, after the reaction is finished, the mixture is centrifuged to obtain precipitate, and the precipitate is dried and crushed after being washed to obtain nano-belt toughened ceramic powder; the nano-belt toughening ceramic powder is Al (OH)3The nanobelt toughens the ceramic powder.
In the preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable, in S03, stirring is carried out for 48 hours at the stirring speed of 600 revolutions per minute. The length of the fine fibrous short filament obtained by the invention is about 10 mm.
The performance indexes of the product in the embodiment are as follows: the oxygen index is more than 60 percent; fire resistance: the surface does not crack at 950 ℃ for 4 h; the water content is less than 1 percent; environmental protection property: no halogen, and meets ROHS standard; no hygroscopicity; the elongation is more than 15 percent.
Example 5
This example differs from example 3 only in that:
the phosphorus-nitrogen flame retardant liquid comprises the following components in percentage by weight:
nitrogen additive: 15% of urea and 5% of guanidine carbonate;
phosphorus additive: tris (acryloyloxyethyl) phosphate: 20 percent;
water-based glue (vinegar acrylic glue): 15 percent;
water: 45 percent.
The performance indexes of the product in the embodiment are as follows: the oxygen index is more than 60 percent; fire resistance: the surface does not crack at 950 ℃ for 4 h; the water content is less than 1 percent; environmental protection property: no halogen, and meets ROHS standard; no hygroscopicity; the elongation is more than 15 percent.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The flame-retardant fire-resistant cable is with compound environmental protection high flame-retardant filling rope, its characterized in that: the filling rope comprises a roving made of waste polyester cotton as a base material of the filling rope, phosphorus-nitrogen water-based flame retardant powder is dispersed in the base material, and a first Mg (OH) is coated outside the base material2Flame retardant glue layer, said Mg (OH)2The powdery flame-retardant layer is sprayed outside the flame-retardant glue layer, and the powdery flame-retardant layer is coated on the outsideSecond Mg (OH)2A flame retardant glue layer, said second Mg (OH)2The outside of the flame-retardant glue layer is coated with a ceramic fire-resistant layer.
2. The composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable according to claim 1, characterized in that: the waste polyester cotton comprises waste clothes and/or quilts.
3. The composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable according to claim 1, characterized in that: the gram weight of the roving is 0.2-0.4g/m, the elongation is more than 15%, and the tensile force is more than 0.5N/10 cm.
4. The composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable according to claim 1, characterized in that: the phosphorus-nitrogen water-based flame retardant powder is formed by drying phosphorus-nitrogen flame retardant liquid;
the phosphorus-nitrogen flame retardant liquid comprises the following components in percentage by weight:
nitrogen additive: one or more of urea, guanidine carbonate and melamine formaldehyde: 15% -20%;
phosphorus additive: one or more of tributyl phosphate, caged dicyclic phosphorus and tris (acryloyloxyethyl) phosphate: 15% -20%;
water-based adhesive: 10% -15%;
water: 40% -50%;
the water-based glue comprises pure acrylic glue, vinyl acetate acrylic glue or styrene-acrylic glue.
5. The composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable according to claim 1, characterized in that: the first Mg (OH)2A flame retardant glue layer and said second Mg (OH)2The flame-retardant glue layers comprise the following components in percentage by weight: mg (OH)2Powder or Al (OH)3Powder + Mg (OH)2Mixture of powders: 70-80% and VAE emulsion or acrylic emulsion: 20 to 30 percent; the Al (OH)3Powder + Mg (OH)2In the mixture of powders, Al (OH)3The mass percentage of the powder is less than50 percent; the Al (OH)3Powder and Mg (OH)2The fineness of the powder is 4000-5000 meshes; the VAE emulsion is ethyl acetate copolymer emulsion.
6. The composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable according to claim 1, characterized in that: the components of the powdery flame-retardant layer comprise: 4000- & 5000 mesh Al (OH)3Powder or Mg (OH)2And (3) powder.
7. The composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable according to claim 1, characterized in that: the ceramic refractory layer comprises the following components in percentage by weight:
30-40% of nanobelt toughened ceramic powder;
10-15% of silica gel;
antimony trioxide: decabromodiphenylethane = 1: 110 to 15 percent;
25 to 30 percent of ethyl acetate
0.05 to 0.1 percent of molybdenum disilicide;
0.05 to 0.1 percent of chromium disilicide;
the coating amount of the ceramic refractory layer is 1-2g/m2。
8. The composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable according to claim 7, characterized in that: the preparation method of the nanobelt toughened ceramic powder comprises the following steps: adding 40-50 g/L of aluminum salt aqueous solution, 20-30% of urea aqueous solution, 80-90% of ethanol aqueous solution and ceramic powder into a high-temperature reaction kettle for hydrothermal reaction; the aqueous aluminum salt solution comprises aluminum sulfate and/or aluminum nitrate; the volume ratio of the aluminum salt aqueous solution to the urea aqueous solution to the ethanol aqueous solution is 1: 10: (2-3); the adding weight of the ceramic powder is 100-120 times of that of the aluminum salt aqueous solution; the temperature of the hydrothermal reaction is 120-130 ℃, the time is at least 12 hours, after the reaction is finished, the mixture is centrifuged to obtain a precipitate, and the precipitate is washed, dried and crushed to obtain nanobelt toughened ceramic powder; the nanobelt toughening potteryThe porcelain powder is Al (OH)3The nanobelt toughens the ceramic powder.
9. The preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable according to any one of claims 1 to 8, characterized by comprising the following steps: the method comprises the following steps:
s01, tearing and crushing waste polyester cotton with different sizes by using a high-speed tearing crusher to generate small blocks, slender block materials and small cotton balls, producing fine fibrous short fibers by using a coarse opener, changing the fine fibrous short fibers into fluffy bodies by using large-bin cotton mixing, collecting by using a fine opener and an air pressure cotton box, carding into nets by using a carding machine, and finally producing 2-3 pieces of roving by air spinning;
s02, immersing the roving in P-N flame-retardant liquid, extruding the roving through P-N flame-retardant liquid to remove excessive water, and feeding into the first Mg (OH)2A flame-retardant glue groove, coating Mg (OH) on the outer part of the roving2The flame-retardant adhesive is extruded by a compression roller, and the surface of the roving is sprayed with dry powder Al (OH)3 Or Mg (OH)2Then enters a second Mg (OH)2The flame-retardant glue groove is extruded by a compression roller and then dried;
s03, the ceramic fire-resistant layer is obtained by dipping ceramic silicon rubber functional liquid, and the preparation method of the ceramic silicon rubber functional liquid comprises the following steps: preparing the nano-belt toughening ceramic powder, silica gel and antimony trioxide according to the proportion: decabromodiphenylethane = 1: 1. adding ethyl acetate, molybdenum disilicide and chromium disilicide into a stirrer, stirring for at least 24 hours at a stirring speed of 400-600 revolutions per minute, and uniformly stirring to obtain a ceramic silicon rubber functional liquid;
and S04, after drying, roughening the surface, dipping the rough yarn into the ceramic silicon rubber functional liquid, and then carrying out surface blade coating, vacuum drying and rolling to obtain the composite environment-friendly high-flame-retardant filling rope for the flame-retardant fire-resistant cable.
10. The preparation method of the composite environment-friendly high-flame-retardant filling rope for the flame-retardant and fire-resistant cable according to claim 9, characterized by comprising the following steps: the power of the high-speed tearing crusher is more than 50kw, and the rotating speed is at least 80 r/min; the power of the coarse opener is 10 kw; the length of the fine fibrous staple fibers is 0.5-10 mm.
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