CN111098557B - High-strength flame-retardant silicon core pipe and preparation method thereof - Google Patents

High-strength flame-retardant silicon core pipe and preparation method thereof Download PDF

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CN111098557B
CN111098557B CN201911401408.9A CN201911401408A CN111098557B CN 111098557 B CN111098557 B CN 111098557B CN 201911401408 A CN201911401408 A CN 201911401408A CN 111098557 B CN111098557 B CN 111098557B
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silicon core
flame retardant
density polyethylene
stirring
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CN111098557A (en
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周波
李敏
梅豪杰
白明明
吕宁
李彬彬
刘赛
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ANHUI HUIYI COMMUNICATION SCIENCE CO LTD
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00Layered products having a non-planar shape
    • B32B1/08Tubular products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29DPRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D23/00Producing tubular articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/022 layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00Layers arrangement
    • B32B2250/24All layers being polymeric
    • B32B2250/242All polymers belonging to those covered by group B32B27/32
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/30Properties of the layers or laminate having particular thermal properties
    • B32B2307/306Resistant to heat
    • B32B2307/3065Flame resistant or retardant, fire resistant or retardant
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00Properties of the layers or laminate
    • B32B2307/50Properties of the layers or laminate having particular mechanical properties
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
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    • C08L2207/062HDPE

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Abstract

The invention discloses a high-strength flame-retardant silicon core pipe which is of a double-layer pipe structure and comprises an inner layer and an outer layer, wherein the outer layer is prepared from the following raw materials in parts by weight: 70-80 parts of high-density polyethylene, 9-13 parts of maleic anhydride grafted high-density polyethylene, 3-4 parts of functional filler, 2-3 parts of composite flame retardant and 2-3 parts of processing aid; the inner layer is prepared from the following raw materials in parts by weight: 60-70 parts of high-density polyethylene, 0.8-1 part of composite flame retardant and 4-5 parts of polydimethylsiloxane; the invention also discloses a preparation method of the silicon core tube. The silicon core pipe has a double-layer pipe structure, adopts high-density polyethylene as a matrix, and is added with functional filler and a composite flame retardant, and the functional filler can improve the strength and the mechanical property of an outer-layer pipe; the composite flame retardant improves the flame retardant property of the outer layer of the silicon core pipe, so that the silicon core pipe with high strength and excellent flame retardant property is obtained, has extremely high use safety performance, and is suitable for optical cable communication network systems.

Description

High-strength flame-retardant silicon core pipe and preparation method thereof
Technical Field
The invention belongs to the technical field of silicon core tubes, and particularly relates to a high-strength flame-retardant silicon core tube and a preparation method thereof.
Background
The silicon core pipe is a novel composite pipeline with the inner wall provided with the colloidal silica solid lubricant, has good sealing performance, chemical corrosion resistance and low engineering cost, is widely applied to optical cable communication network systems of highways, railways and the like, and the HDPE silicon core pipe is a novel composite pipeline with the inner wall provided with the colloidal silica solid lubricant, and is called a silicon pipe for short. The composite material is extruded and compounded by three plastic extruders synchronously, the main raw material is high-density polyethylene, and the core layer is solid lubricant silica gel with the lowest friction coefficient. The method is widely applied to optical cable communication network systems. The silicon core tube needs to have flame retardant performance, otherwise when the short circuit of inside cable takes place, very easily causes the burning phenomenon, influences safety in utilization.
Chinese patent No. CN02112744.1 discloses a special material for halogen-free flame-retardant silicon core tube and its preparation method, wherein the disclosed components contain 25-45% of composite halogen-free flame retardant (ANT-6/Mg (OH))2) The main component of the composite halogen-free flame retardant is powdery metal hydrate, which belongs to one of mineral substances; because the powdery mineral has the characteristic of poor dispersion; therefore, after the halogen-free flame retardant is added into a silicon core pipe as a main component, the halogen-free flame retardant is unevenly dispersed in the component, so that the problems of poor mechanical property, high hardness and high brittleness of the finished product of the flame-retardant silicon core pipe are caused.
Disclosure of Invention
The invention aims to provide a high-strength flame-retardant silicon core pipe and a preparation method thereof, wherein the silicon core pipe is of a double-layer pipe structure, the outer layer adopts high-density polyethylene as a matrix, functional filler and a composite flame retardant are added, and the functional filler can be uniformly distributed in an HDPE matrix after being modified, so that the strength and the mechanical property of the outer-layer pipe are improved; the composite flame retardant not only has multi-level flame retardant performance, but also has good compatibility with a matrix, can be uniformly distributed in the matrix, improves the flame retardant performance of the outer layer of the silicon core tube, and effectively resists external combustion; the composite flame retardant is also added into the inner layer material, so that the combustion phenomenon caused by short circuit of a cable arranged inside the silicon core pipe can be effectively prevented, and the use safety of the silicon core pipe is improved; the silicon core tube prepared by the invention has high strength and excellent flame retardant property, has extremely high use safety performance, and is suitable for optical cable communication network systems.
The purpose of the invention can be realized by the following technical scheme
The high-strength flame-retardant silicon core pipe is of a double-layer pipe structure and comprises an inner layer and an outer layer, wherein the outer layer is prepared from the following raw materials in parts by weight: 70-80 parts of high-density polyethylene, 9-13 parts of maleic anhydride grafted high-density polyethylene, 3-4 parts of functional filler, 2-3 parts of composite flame retardant and 2-3 parts of processing aid;
the inner layer is prepared from the following raw materials in parts by weight: 60-70 parts of high-density polyethylene, 0.8-1 part of composite flame retardant and 4-5 parts of polydimethylsiloxane.
Further, the processing aid comprises oleamide, glyceryl monostearate and an antioxidant, wherein the mass ratio of the oleamide to the glyceryl monostearate to the antioxidant is 1:1: 0.5.
Further, the functional filler is prepared by the following method:
(1) weighing carbon fibers, dispersing the carbon fibers in dilute nitric acid, stirring for 10-12h at 75 ℃, filtering and washing to be neutral, then stirring the carbon fibers washed by the dilute nitric acid in a mixed solution of concentrated sulfuric acid and concentrated nitric acid for 20-22h at 60 ℃, repeatedly diluting, standing, washing with deionized water to be neutral, and centrifugally filtering to obtain pretreated carbon fibers;
(2) weighing 1g of pretreated carbon fiber, placing the pretreated carbon fiber in 500mL of deionized water, performing water bath ultrasonic treatment for 12h, and performing probe ultrasonic treatment for 13-15 min;
(3) pouring the obtained suspension into 500mL of Tris-HCl buffer solution, then adding 0.57g of 3, 4-dihydroxyphenethylamine hydrochloride, and stirring at room temperature for 120-130 min;
(4) centrifuging the suspension at 7500rpm for 20-25min, washing the slurry with acetone, centrifuging to remove solvent, repeating washing and centrifuging steps for 4-5 times, and freeze drying the precipitate for 48h to obtain functional filler;
further, the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid in the mixed solution of the concentrated sulfuric acid and the concentrated nitric acid in the step (1) is 3: 1.
further, the composite flame retardant is prepared by the following method:
(1) adding 200-250mL of 5 mass percent NaOH solution and 30g of cellulose into a round-bottom three-mouth flask, stirring at the normal temperature at 150r/min for 26-30min, heating to 92-94 ℃, adding 24-28mL of formaldehyde solution, and stirring for reacting for 60-70 min;
(2) weighing 11.8-12.4g of p-phenylenediamine, adding the p-phenylenediamine into the mixed solution, and continuously stirring for reaction at the temperature of 92-94 ℃ for 120-130 min;
(3) adding 25-27g of TCPP and 300mg of sodium dodecyl benzene sulfonate into the reaction solution, and stirring for 3Adding 22.6-22.9g of aluminum nitrate into the mixed solution after 0min, stirring, reacting for 30min, and then dropwise adding 7.7-7.8g of H3PO4Continuing to react for 30 min;
(4) and standing the product at room temperature for 12h, filtering, washing, drying at 80 ℃ to constant volume, grinding, and sieving with a 200-mesh sieve to obtain the composite flame retardant.
A preparation method of a high-strength flame-retardant silicon core tube comprises the following steps:
firstly, mixing maleic anhydride grafted high-density polyethylene, functional filler, composite flame retardant, processing aid and 1/5 high-density polyethylene in outer layer raw materials, heating to 120-130 ℃, stirring and mixing for 25-30min, then adding the rest high-density polyethylene, continuously mixing for 40-50min at 120-130 ℃, and cooling to below 50 ℃ for later use;
thirdly, taking the raw materials of the inner layer, heating to 105-120 ℃, stirring and mixing for 40-50min, and cooling to below 50 ℃ for later use;
step four, respectively heating and melting the outer layer raw material and the inner layer raw material, and then synchronously extruding and compounding the raw materials through two extruders to obtain a silicon core tube blank, wherein the temperature during extrusion is controlled to be 175-185 ℃;
and fifthly, performing vacuum shaping, cooling, traction and coiling on the silicon core pipe blank to obtain the silicon core pipe.
The invention has the advantages of
The functional filler is added into the outer raw material of the silicon core tube, the functional filler is prepared by modifying carbon fiber, after the carbon fiber is subjected to acidification treatment by sulfuric acid and nitric acid, OH on the surface of a molecule is oxidized into COOH, and the COOH can react with OH on a 3, 4-dihydroxyphenylethylamine hydrochloride molecule, so that the 3, 4-dihydroxyphenylethylamine hydrochloride is grafted on the carbon fiber, and then the 3, 4-dihydroxyphenylethylamine hydrochloride is subjected to polymerization reaction on the surface of the carbon fiber to form a layer of polymer which is attached to the surface of the carbon fiber and polymerized on the surface of the carbon fiber to form a layer of polymer, wherein the polymer layer has good compatibility with HDPE, so that the carbon fiber can be uniformly dispersed in an HDPE matrix, and the dispersibility of the carbon fiber is improved; the Carbon Fiber (CF) has the characteristics of high strength and modulus, low density, small linear expansion coefficient and the like, the Young modulus of the carbon fiber is more than 3 times that of the glass fiber, but the density is only 2/3 of the carbon fiber, and the carbon fiber is uniformly dispersed in the HDPE matrix, so that the reinforcing effect can be effectively exerted, and the strength of the pipe is improved;
the composite flame retardant, namely-NH on p-phenylenediamine, is added into the raw materials of the outer layer and the inner layer of the silicon core tube2Reacting with-OH on the surface of cellulose molecules, grafting the cellulose molecules onto the cellulose molecules, carrying out Mannich reaction on the cellulose molecules and formaldehyde to generate a prepolymer on the surface of the cellulose, and preparing a composite flame retardant by a reverse precipitation method, wherein the composite flame retardant contains TCPP, aluminum phosphate and other effective components and has a multi-layer flame retardant effect; TCPP is used as a phosphorus-halogen synergistic flame retardant, phosphoric anhydride or phosphoric acid with strong dehydration effect is generated through pyrolysis, and the phosphoric anhydride or the phosphoric acid can promote cellulose dehydration to form a compact carbon layer to cover the surface of the base material; meanwhile, the pyrolysis of the aluminum phosphate can also dilute the temperature of the combustion zone, and the formed alumina covers the surface of the matrix material, so that an excellent flame retardant effect is achieved under the combined action of the carbon layer and the alumina; in addition, the outer layer of the composite flame retardant has a polymer molecular chain, the polymer molecular chain also has a benzene ring and a carbon chain, and the composite flame retardant has good compatibility with a polyethylene matrix, can overcome the defect that an inorganic flame retardant is difficult to disperse, is uniformly distributed in a pipe, and fully exerts the flame retardant property; the outer layer and the inner layer are both added with a flame retardant, the outer layer has flame retardant performance and can effectively resist external combustion, the inner layer has flame retardant performance, the combustion phenomenon caused by short circuit of an internal cable arranged inside the silicon core pipe can be effectively prevented, and the use safety of the silicon core pipe is improved;
the silicon core pipe has a double-layer pipe structure, the outer layer adopts high-density polyethylene as a matrix, functional filler and composite flame retardant are added, and the functional filler can be uniformly distributed in the HDPE matrix after modification treatment, so that the strength and the mechanical property of the outer-layer pipe are improved; the composite flame retardant not only has multi-level flame retardant performance, but also has good compatibility with a matrix, can be uniformly distributed in the matrix, improves the flame retardant performance of the outer layer of the silicon core tube, and effectively resists external combustion; the composite flame retardant is also added into the inner layer material, so that the combustion phenomenon caused by short circuit of a cable arranged inside the silicon core pipe can be effectively prevented, and the use safety of the silicon core pipe is improved; the silicon core tube prepared by the invention has high strength and excellent flame retardant property, has extremely high use safety performance, and is suitable for optical cable communication network systems.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A high-strength flame-retardant silicon core pipe is of a double-layer pipe structure and comprises an inner layer and an outer layer;
the outer layer is prepared from the following raw materials in parts by weight: 70-80 parts of high-density polyethylene (HDPE), 9-13 parts of maleic anhydride grafted high-density polyethylene, 3-4 parts of functional filler, 2-3 parts of composite flame retardant and 2-3 parts of processing aid;
the inner layer is prepared from the following raw materials in parts by weight: 60-70 parts of high-density polyethylene, 0.8-1 part of composite flame retardant and 4-5 parts of polydimethylsiloxane;
the processing aid comprises oleamide, glyceryl monostearate and an antioxidant, wherein the mass ratio of the oleamide to the glyceryl monostearate to the antioxidant is 1:1: 0.5; the antioxidant is common antioxidant for polyethylene, such as antioxidant 1076, antioxidant CA, etc.;
the functional filler is prepared by the following method:
(1) weighing carbon fibers, dispersing the carbon fibers in dilute nitric acid, stirring for 10-12h at 75 ℃, filtering and washing to be neutral, then stirring the carbon fibers subjected to dilute nitric acid pickling in a mixed solution of concentrated sulfuric acid and concentrated nitric acid (volume ratio is 3: 1) for 20-22h at 60 ℃, repeatedly diluting and standing the product, washing the product to be neutral by deionized water, and performing centrifugal filtration to obtain pretreated carbon fibers;
(2) weighing 1g of pretreated carbon fiber, placing the pretreated carbon fiber in 500mL of deionized water, performing water bath ultrasonic treatment for 12h, and performing probe ultrasonic treatment for 13-15 min;
(3) the obtained suspension was poured into 500mL of Tris-HCl buffer (pH 8.5), then 0.57g of 3, 4-dihydroxyphenethylamine hydrochloride was added, and stirred at room temperature for 120-;
(4) centrifuging the suspension at 7500rpm for 20-25min, washing the slurry with acetone, centrifuging to remove solvent, repeating washing and centrifuging steps for 4-5 times, and freeze drying the precipitate for 48h to obtain functional filler;
after the carbon fiber is acidified by sulfuric acid and nitric acid, OH on the surface of the molecule is oxidized into COOH, the COOH can react with OH on the molecule of 3, 4-dihydroxyphenylethylamine hydrochloride, so that the 3, 4-dihydroxyphenylethylamine hydrochloride is grafted on the carbon fiber, and the 3, 4-dihydroxyphenylethylamine hydrochloride is subjected to polymerization reaction on the surface of the carbon fiber to form a layer of polymer which is attached to the surface of the carbon fiber and polymerized on the surface of the carbon fiber to form a layer of polymer; the Carbon Fiber (CF) has the characteristics of high strength and modulus, low density, small linear expansion coefficient and the like, the Young modulus of the carbon fiber is more than 3 times that of the glass fiber, but the density is only 2/3 of the carbon fiber, and the carbon fiber is uniformly dispersed in the HDPE matrix, so that the reinforcing effect can be effectively exerted, and the strength of the pipe is improved;
the composite flame retardant is prepared by the following method:
(1) adding 200-250mL of 5 mass percent NaOH solution and 30g of cellulose into a round-bottom three-mouth flask, stirring at the normal temperature at 150r/min for 26-30min, heating to 92-94 ℃, adding 24-28mL of formaldehyde solution, and stirring for reacting for 60-70 min;
(2) weighing 11.8-12.4g of p-phenylenediamine, adding the p-phenylenediamine into the mixed solution, and continuously stirring for reaction at the temperature of 92-94 ℃ for 120-130 min;
(3) adding 25-27g of TCPP (tris (chloroisopropyl) phosphate) and 300mg of sodium dodecyl benzene sulfonate into the reaction solution, stirring for 30min, then adding 22.6-22.9g of aluminum nitrate into the mixed solution, stirring, reacting for 30min, and then dropwise adding 7.7-7.8g of H3PO4Continuing to react for 30 min;
(4) standing the product at room temperature for 12h, filtering, washing, drying at 80 ℃ to constant volume, grinding, and sieving with a 200-mesh sieve to obtain the composite flame retardant;
-NH on p-phenylenediamine2Reacting with-OH on the surface of cellulose molecules, grafting the cellulose molecules onto the cellulose molecules, carrying out Mannich reaction on the cellulose molecules and formaldehyde to generate a prepolymer on the surface of the cellulose, and preparing a composite flame retardant by a reverse precipitation method, wherein the composite flame retardant contains TCPP, aluminum phosphate and other effective components and has a multi-layer flame retardant effect; TCPP is used as a phosphorus-halogen synergistic flame retardant, phosphoric anhydride or phosphoric acid with strong dehydration effect is generated through pyrolysis, and the phosphoric anhydride or the phosphoric acid can promote cellulose dehydration to form a compact carbon layer to cover the surface of the base material; meanwhile, the pyrolysis of the aluminum phosphate can also dilute the temperature of the combustion zone, and the formed alumina covers the surface of the matrix material, so that an excellent flame retardant effect is achieved under the combined action of the carbon layer and the alumina; in addition, the outer layer of the composite flame retardant has a polymer molecular chain, the polymer molecular chain also has a benzene ring and a carbon chain, and the composite flame retardant has good compatibility with a polyethylene matrix, can overcome the defect that an inorganic flame retardant is difficult to disperse, is uniformly distributed in a pipe, and fully exerts the flame retardant property;
the preparation method of the silicon core tube comprises the following steps:
firstly, mixing maleic anhydride grafted high-density polyethylene, functional filler, composite flame retardant, processing aid and 1/5 high-density polyethylene in outer layer raw materials, heating to 120-130 ℃, stirring and mixing for 25-30min, then adding the rest high-density polyethylene, continuously mixing for 40-50min at 120-130 ℃, and cooling to below 50 ℃ for later use;
thirdly, taking the raw materials of the inner layer, heating to 105-120 ℃, stirring and mixing for 40-50min, and cooling to below 50 ℃ for later use;
step four, respectively heating and melting the outer layer raw material and the inner layer raw material, and then synchronously extruding and compounding the raw materials through two extruders to obtain a silicon core tube blank, wherein the temperature during extrusion is controlled to be 175-185 ℃;
and fifthly, performing vacuum shaping, cooling, traction and coiling on the silicon core pipe blank to obtain the silicon core pipe.
Example 1
A high-strength flame-retardant silicon core pipe is of a double-layer pipe structure and comprises an inner layer and an outer layer;
the outer layer is prepared from the following raw materials in parts by weight: 70 parts of high-density polyethylene, 9 parts of maleic anhydride grafted high-density polyethylene, 3 parts of functional filler, 2 parts of composite flame retardant and 2 parts of processing aid;
the inner layer is prepared from the following raw materials in parts by weight: 60 parts of high-density polyethylene, 0.8-1 part of composite flame retardant and 4 parts of polydimethylsiloxane;
the silicon core tube is prepared by the following steps:
firstly, mixing maleic anhydride grafted high-density polyethylene, functional filler, composite flame retardant, processing aid and 1/5 high-density polyethylene in outer layer raw materials, heating to 120 ℃, stirring and mixing for 25min, adding the rest high-density polyethylene, continuously mixing for 40min at 120 ℃, and cooling to below 50 ℃ for later use;
thirdly, taking each raw material of the inner layer, heating to 105 ℃, stirring and mixing for 40min, and cooling to below 50 ℃ for later use;
step four, respectively heating and melting the outer layer raw material and the inner layer raw material, and then synchronously extruding and compounding the raw materials through two extruders to obtain a silicon core pipe blank, wherein the temperature during extrusion is controlled at 175 ℃;
and fifthly, performing vacuum shaping, cooling, traction and coiling on the silicon core pipe blank to obtain the silicon core pipe.
Example 2
A high-strength flame-retardant silicon core pipe is of a double-layer pipe structure and comprises an inner layer and an outer layer;
the outer layer is prepared from the following raw materials in parts by weight: 75 parts of high-density polyethylene, 11 parts of maleic anhydride grafted high-density polyethylene, 3.5 parts of functional filler, 2.5 parts of composite flame retardant and 2.5 parts of processing aid;
the inner layer is prepared from the following raw materials in parts by weight: 65 parts of high-density polyethylene, 0.9 part of composite flame retardant and 4.5 parts of polydimethylsiloxane;
the silicon core tube is prepared by the following steps:
firstly, mixing maleic anhydride grafted high-density polyethylene, functional filler, composite flame retardant, processing aid and 1/5 high-density polyethylene in outer layer raw materials, heating to 125 ℃, stirring and mixing for 28min, then adding the rest high-density polyethylene, continuously mixing for 45min at 125 ℃, and cooling to below 50 ℃ for later use;
thirdly, taking each raw material of the inner layer, heating to 112 ℃, stirring and mixing for 45min, and cooling to below 50 ℃ for later use;
step four, respectively heating and melting the outer layer raw material and the inner layer raw material, and then synchronously extruding and compounding the raw materials through two extruders to obtain a silicon core pipe blank, wherein the temperature during extrusion is controlled at 180 ℃;
and fifthly, performing vacuum shaping, cooling, traction and coiling on the silicon core pipe blank to obtain the silicon core pipe.
Example 3
A high-strength flame-retardant silicon core pipe is of a double-layer pipe structure and comprises an inner layer and an outer layer;
the outer layer is prepared from the following raw materials in parts by weight: 80 parts of high-density polyethylene, 13 parts of maleic anhydride grafted high-density polyethylene, 4 parts of functional filler, 3 parts of composite flame retardant and 3 parts of processing aid;
the inner layer is prepared from the following raw materials in parts by weight: 70 parts of high-density polyethylene, 1 part of composite flame retardant and 5 parts of polydimethylsiloxane;
the silicon core tube is prepared by the following steps:
firstly, mixing maleic anhydride grafted high-density polyethylene, functional filler, composite flame retardant, processing aid and 1/5 high-density polyethylene in outer layer raw materials, heating to 130 ℃, stirring and mixing for 30min, adding the rest high-density polyethylene, continuously mixing for 50min at 130 ℃, and cooling to below 50 ℃ for later use;
thirdly, taking each raw material of the inner layer, heating to 120 ℃, stirring and mixing for 50min, and cooling to below 50 ℃ for later use;
step four, respectively heating and melting the outer layer raw material and the inner layer raw material, and then synchronously extruding and compounding the raw materials through two extruders to obtain a silicon core pipe blank, wherein the temperature during extrusion is controlled at 185 ℃;
and fifthly, performing vacuum shaping, cooling, traction and coiling on the silicon core pipe blank to obtain the silicon core pipe.
Comparative example 1
The functional filler in the outer layer raw material of example 1 was changed to carbon fiber, and the rest of the raw materials and the preparation process were unchanged.
Comparative example 2
The functional filler in the outer layer raw material of example 1 was removed, and the rest of the raw materials and the preparation process were unchanged.
Comparative example 3
The flame retardant in the raw materials of example 1 was replaced by TCPP, and the rest of the raw materials and the preparation process were unchanged.
The silicon core pipes obtained in examples 1 to 3 and comparative examples 1 to 3 were subjected to the following performance tests, in which the hardness of the outer wall of the pipe was measured according to the method specified in GB/T2411, the tensile yield strength and the maximum tensile load strength of the pipe were measured according to GB/T8804.1-2003, and the flame retardancy was measured by a Limiting Oxygen Index (LOI) and a vertical burning (UL-94) using a JF-3 Limiting Oxygen Index (LOI) meter and a CZF-II vertical burning tester, respectively, and the results are shown in Table 1 below:
TABLE 1
Figure BDA0002347541860000111
From the above table 1, it can be seen that the hardness value of the silicon core tube prepared in the examples 1 to 3 is 55.8 to 56.5, the yield strength value is 25.6 to 25.9, and the traction load value is 5300-; the LOI value of the silicon core tube prepared in the embodiment 1-3 is 27.5-28.2, and the vertical combustion grades are all V-0 grade, which shows that the silicon core tube material prepared by the invention has good flame retardant property; compared with comparative examples 1 and 2, the modified carbon fiber is prepared into the functional filler which can be uniformly dispersed in the HDPE matrix, so that the mechanical property of the pipe is improved; compared with comparative example 3, the composite flame retardant prepared by the method is added into a pipe material, has a multi-layer flame retardant effect, and can be uniformly distributed in the pipe material, so that the flame retardant property of the silicon core pipe is improved;
the silicon chip tube is processed to phi 32/26 specification, and the silicon chip tube prepared in examples 1-3 is tested for the physicochemical properties according to JTT 496 and 2004 high density polyethylene silicon chip plastic tube for underground road communication pipelines, and the test results are as follows:
TABLE 2
Figure BDA0002347541860000112
Figure BDA0002347541860000121
As can be seen from the above table 2, the silicon core tube prepared in the embodiments 1-3 of the present invention all meet the standard of JTT 496-; in addition, according to the national communication industry YD/T841-1996 plastic pipe for underground communication pipeline, YD5043-1997 temporary regulations on acceptance of plastic pipeline engineering of long-distance communication optical cables and JT/TEM02-2000 high-density polyethylene silicon core plastic pipe issued by the department of transportation, 16 technical indexes such as the structural size, the ring stiffness, the flat test and the like are detected, and all the indexes meet the requirements; the silicon core tube prepared by the invention has good mechanical property and high flame retardant property, meets various use requirements, and is suitable for optical cable communication network systems.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims (3)

1. The utility model provides a fire-retardant silicon core pipe of high strength, is double-deck tubular construction, includes inlayer and skin, its characterized in that, the skin is made by following part by weight raw materials: 70-80 parts of high-density polyethylene, 9-13 parts of maleic anhydride grafted high-density polyethylene, 3-4 parts of functional filler, 2-3 parts of composite flame retardant and 2-3 parts of processing aid;
the inner layer is prepared from the following raw materials in parts by weight: 60-70 parts of high-density polyethylene, 0.8-1 part of composite flame retardant and 4-5 parts of polydimethylsiloxane;
the functional filler is prepared by the following method:
(1) weighing carbon fibers, dispersing the carbon fibers in dilute nitric acid, stirring for 10-12h at 75 ℃, filtering and washing to be neutral, then stirring the carbon fibers washed by the dilute nitric acid in a mixed solution of concentrated sulfuric acid and concentrated nitric acid for 20-22h at 60 ℃, repeatedly diluting, standing, washing with deionized water to be neutral, and centrifugally filtering to obtain pretreated carbon fibers; the volume ratio of concentrated sulfuric acid to concentrated nitric acid in the mixed solution of concentrated sulfuric acid and concentrated nitric acid is 3: 1;
(2) weighing 1g of pretreated carbon fiber, placing the pretreated carbon fiber in 500mL of deionized water, performing water bath ultrasonic treatment for 12h, and performing probe ultrasonic treatment for 13-15 min;
(3) pouring the obtained suspension into 500mL of Tris-HCl buffer solution, then adding 0.57g of 3, 4-dihydroxyphenethylamine hydrochloride, and stirring at room temperature for 120-130 min;
(4) centrifuging the suspension at 7500rpm for 20-25min, washing the slurry with acetone, centrifuging to remove solvent, repeating washing and centrifuging steps for 4-5 times, and freeze drying the precipitate for 48h to obtain functional filler;
the composite flame retardant is prepared by the following method:
(1) adding 200-250mL of 5 mass percent NaOH solution and 30g of cellulose into a round-bottom three-mouth flask, stirring at the normal temperature at 150r/min for 26-30min, heating to 92-94 ℃, adding 24-28mL of formaldehyde solution, and stirring for reacting for 60-70 min;
(2) weighing 11.8-12.4g of p-phenylenediamine, adding the p-phenylenediamine into the mixed solution, and continuously stirring for reaction at the temperature of 92-94 ℃ for 120-130 min;
(3) adding 25-27g of TCPP and 30g of TCPP into the reaction solution0mg sodium dodecyl benzene sulfonate, stirring for 30min, then adding 22.6-22.9g aluminum nitrate into the mixed solution, stirring, reacting for 30min, and then dropwise adding 7.7-7.8g of H3PO4Continuing to react for 30 min;
(4) and standing the product at room temperature for 12h, filtering, washing, drying at 80 ℃ to constant volume, grinding, and sieving with a 200-mesh sieve to obtain the composite flame retardant.
2. The high-strength flame-retardant silicon core tube as recited in claim 1, wherein the processing aid comprises oleamide, glyceryl monostearate and an antioxidant, and the mass ratio of the oleamide, the glyceryl monostearate and the antioxidant is 1:1: 0.5.
3. The method for preparing the high-strength flame-retardant silicon core tube according to claim 1, which is characterized by comprising the following steps:
firstly, mixing maleic anhydride grafted high-density polyethylene, functional filler, composite flame retardant, processing aid and 1/5 high-density polyethylene in outer layer raw materials, heating to 120-130 ℃, stirring and mixing for 25-30min, then adding the rest high-density polyethylene, continuously mixing for 40-50min at 120-130 ℃, and cooling to below 50 ℃ for later use;
thirdly, taking the raw materials of the inner layer, heating to 105-120 ℃, stirring and mixing for 40-50min, and cooling to below 50 ℃ for later use;
step four, respectively heating and melting the outer layer raw material and the inner layer raw material, and then synchronously extruding and compounding the raw materials through two extruders to obtain a silicon core tube blank, wherein the temperature during extrusion is controlled to be 175-185 ℃;
and fifthly, performing vacuum shaping, cooling, traction and coiling on the silicon core pipe blank to obtain the silicon core pipe.
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