CN116239835B - High-strength polyethylene water supply pipe and preparation method thereof - Google Patents
High-strength polyethylene water supply pipe and preparation method thereof Download PDFInfo
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- CN116239835B CN116239835B CN202310526164.7A CN202310526164A CN116239835B CN 116239835 B CN116239835 B CN 116239835B CN 202310526164 A CN202310526164 A CN 202310526164A CN 116239835 B CN116239835 B CN 116239835B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D23/00—Producing tubular articles
- B29D23/001—Pipes; Pipe joints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L57/00—Protection of pipes or objects of similar shape against external or internal damage or wear
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L9/00—Rigid pipes
- F16L9/12—Rigid pipes of plastics with or without reinforcement
- F16L9/133—Rigid pipes of plastics with or without reinforcement the walls consisting of two layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
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Abstract
The invention relates to the technical field of composite water supply pipes, in particular to a high-strength polyethylene water supply pipe and a preparation method thereof, and the preparation method comprises the following processes: taking high-density polyethylene, zinc oxide and a processing aid as inner layer raw materials, taking modified polyethylene, modified calcium sulfate whisker and the processing aid as outer layer raw materials, and performing double-layer co-extrusion to form an inner layer and an outer layer to obtain a polyethylene water supply pipe; the high-density polyethylene in the outer layer raw material is crosslinked with epoxy resin with unsaturated double bonds under the action of a peroxide crosslinking agent, and the calcium sulfate whisker is modified by an amino coupling agent. The invention adopts high-density polyethylene with strength as main resin component of the water supply pipe, and nano zinc oxide and calcium sulfate whisker are respectively added into raw materials of an inner layer and an outer layer of the polyethylene water supply pipe as reinforcing agents, thereby playing the roles of physical crosslinking and heterogeneous nucleation and improving the mechanical property of the prepared polyethylene water supply pipe.
Description
Technical Field
The invention relates to the technical field of composite water supply pipes, in particular to a high-strength polyethylene water supply pipe and a preparation method thereof.
Background
Polyethylene is thermoplastic engineering plastics which are polymerized by ethylene and butadiene under the action of catalyst. As one of polyethylene systems, high Density Polyethylene (HDPE) has good hardness, tensile strength, creep property and the like, and is suitable for being widely applied to the field of water supply pipe manufacturing. The water supply pipe is used as a pipeline for a pipe network, and is suitable for the fields of water supply and drainage, chemical industry, pollution discharge, reconstruction of water works, national hydraulic engineering and the like. The polyethylene is taken as the resin component of the water supply pipe, and the prepared polyethylene pipe has the advantages of non-toxic material, light weight, difficult scaling and rust in long-term use, smooth inner wall of the pipe, no change with time and capability of keeping good water quality for a long time. In order to meet various environmental demands, the mechanical property demands of people on the polyethylene water supply pipe are gradually increased. Therefore, we propose a high strength polyethylene water supply pipe and a method for preparing the same.
Disclosure of Invention
The invention aims to provide a high-strength polyethylene water supply pipe and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: the preparation method of the high-strength polyethylene water supply pipe comprises the following steps:
taking high-density polyethylene, zinc oxide and a processing aid as inner layer raw materials, taking modified polyethylene, modified calcium sulfate whisker and the processing aid as outer layer raw materials, and performing double-layer co-extrusion to form an inner layer and an outer layer to obtain a polyethylene water supply pipe;
the modified polyethylene in the outer layer raw material is prepared by crosslinking high-density polyethylene with epoxy resin with unsaturated double bonds under the action of a peroxide crosslinking agent, and the modified calcium sulfate whisker is prepared by modifying calcium sulfate whisker by an amino coupling agent.
Further, the processing aid is a mixture of two or more of a coupling agent, a dispersing agent, a masterbatch and an antioxidant.
Further, the inner layer raw materials comprise the following components in parts by mass: 92-98 parts of high-density polyethylene, 4.6-4.9 parts of zinc oxide, 0.8-1.0 part of coupling agent and 0.4-0.5 part of dispersing agent;
further, the outer layer raw materials comprise the following components in parts by mass: 90 to 100 parts of modified polyethylene, 9 to 10 parts of modified calcium sulfate whisker, 0.8 to 1.0 part of antioxidant and 2 to 3 parts of color master batch.
High density polyethylene: YGH041, melt Mass Flow Rate (MFR) 0.4g/10min, from China petrochemical Shanghai petrochemical Co., ltd;
zinc oxide: nanoscale, 100nm particle size, from Beijing De island gold technology Co., ltd;
coupling agent: titanate coupling agent from Nanjing Netherlands New Material technology Co;
the dispersing agent is polyethylene wax: SX-100B is derived from the petrifaction of Yanshan;
calcium sulfate whisker: B6W556, from bokey ecological engineering, inc;
the antioxidant is antioxidant 1010, which is derived from Basiff (China) Limited company;
color master batch: from Kunshan color plastic pigment Inc.
Further, the inner layer raw material is prepared by the following process:
mixing zinc oxide, a coupling agent and a dispersing agent in a high-speed stirrer, stirring at a high speed at 115-125 ℃ for 5-10 min, and vacuum drying for 100-150 min;
mixing with high-density polyethylene, stirring, extruding in a double-screw extruder, granulating at 170-210 deg.C, and drying for 24 hr.
In the technical scheme, zinc oxide is dispersed in high-density polyethylene, so that molecular chain segment movement of the zinc oxide can be restrained, and a physical crosslinking effect is achieved, and the yield strength of the prepared inner layer is improved. Meanwhile, zinc oxide can play a heterogeneous nucleation role, promote the improvement of the crystallinity of the high-density polyethylene, reduce the grain size of the high-density polyethylene, and improve the tensile strength of the prepared inner layer. Before the zinc oxide is used, the zinc oxide is stirred with a coupling agent (titanate coupling agent) and a dispersing agent (polyethylene wax) at a high speed, and the surface modification of the zinc oxide is realized by utilizing high shearing acting force. The modified zinc oxide has good interface compatibility with high-density polyethylene, and can further improve the mechanical properties of the prepared inner layer.
Further, the outer layer raw material is prepared by the following process:
preparation of epoxy resin in the step (1):
taking 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone and epichlorohydrin, adding n-butanol and benzyl trimethyl ammonium bromide, mixing, heating to 100-120 ℃, reacting for 3-4 h, and rotary steaming; the temperature of the system is reduced to 70-75 ℃, and sodium hydroxide solution is added for reaction for 4-6 h; adding distilled water and toluene, stirring, standing for layering, taking a resin layer, washing to be neutral, steaming in a rotary mode, adding ethyl acetate, taking a liquid phase, and drying to constant weight to obtain epoxy resin;
and (2) preparing modified polyethylene:
vacuum drying high-density polyethylene at 70 ℃ for 24 hours for dehydration; adding peroxide cross-linking agent and degradation inhibitor into acetone for dissolution, mixing with high-density polyethylene and epoxy resin, and uniformly mixing in a high-speed stirrer after the acetone volatilizes; extruding and granulating in a double-screw extruder at 170-220 deg.c and drying for 24 hr to obtain modified polyethylene;
and (3) preparing modified calcium sulfate whiskers:
mixing an amino coupling agent, absolute ethyl alcohol and distilled water, adding calcium sulfate whiskers, stirring, and carrying out forced air drying at 100 ℃ for 4 hours to obtain modified calcium sulfate whiskers;
and (4) preparing an outer layer raw material:
mixing the modified polyethylene, the antioxidant, the color masterbatch and the modified calcium sulfate whisker, extruding and granulating in a double-screw extruder, wherein the extruding temperature is 165-200 ℃, and drying for 24 hours to obtain the outer layer raw material.
In the step (1), the molar ratio of 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone to epichlorohydrin is 1 (9.5-10.5);
the molar ratio of 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone to sodium hydroxide is 1 (2.8-3.2);
the dosage of the benzyl trimethyl ammonium bromide is 1.8 to 2.5 percent of the mass of the 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone;
the mass concentration of the sodium hydroxide solution is 30-35%.
Further, in the step (2), the mass ratio of the high-density polyethylene, the epoxy resin, the acetone, the degradation inhibitor tetramethylthiuram disulfide and the cross-linking agent benzoyl peroxide is 100 (5-12): 10-12): 0.1-0.2): 0.2-0.5.
Further, in the step (3), the amino coupling agent is KH-540 or KH-550;
the mass ratio of the calcium sulfate whisker to the amino coupling agent is 100 (3.0-5.0);
the mass ratio of the amino coupling agent to the absolute ethyl alcohol to the distilled water is 1:90:10.
Further, in the step (4), the outer layer raw materials comprise the following components in mass percent: 90 to 100 parts of modified high-density polyethylene, 9 to 10 parts of modified calcium sulfate whisker, 0.8 to 1.0 part of antioxidant and 2 to 3 parts of color master batch.
In the technical scheme, the calcium sulfate whisker is dispersed in the high-density polyethylene and used as a physical crosslinking point, so that the mechanical property of the outer layer of the prepared polyethylene water supply pipe can be improved; and the heterogeneous nucleation is exerted to change the movement mode of molecular chains, form a space as a main effect, and improve the crystallinity of the high-density polyethylene, so that the mechanical property of the outer layer of the prepared polyethylene water supply pipe is improved.
3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone and epoxy chloropropane are subjected to ring opening of epoxy groups and hydroxyl grafting in a phenol structure under the action of a phase transfer catalyst of benzyl trimethyl ammonium bromide to generate etherification, and then a product obtained by the previous reaction is subjected to ring closing under the action of sodium hydroxide to form epoxy groups, so that the epoxy resin with polyunsaturated double bonds is prepared. Then under the action of a cross-linking agent benzoyl peroxide, the epoxy resin grafted polyethylene and self-crosslinking are initiated, a branched chain with an epoxy group is introduced into a polyethylene molecular chain, and the molecular weight of the high-density polyethylene is increased, so that the strength and rigidity of the prepared modified polyethylene are improved; and the phenyl ether structure in the epoxy resin is helpful for improving the impact resistance of the outer layer. The degradation inhibitor in the system can relieve the degradation of the peroxide crosslinking agent on the high-density polyethylene, effectively control the crosslinking reaction of the high-density polyethylene and realize the improvement of the mechanical property of the modified polyethylene.
In the subsequent preparation of the polyethylene water supply pipe, the modified polyethylene in the outer layer raw material is melted at the coextrusion temperature and reacts with the amino coupling agent on the surface of the modified calcium sulfate whisker, so that the epoxy resin structure in the modified polyethylene is crosslinked and solidified to form a three-dimensional reticular structure, the rigidity of the prepared outer layer is improved, and the outer layer strength in the polyethylene water supply pipe is effectively improved.
Compared with the prior art, the invention has the following beneficial effects:
1. the high-strength polyethylene water supply pipe and the preparation method thereof adopt high-density polyethylene with strength as a main resin component of the water supply pipe, nano zinc oxide and calcium sulfate whisker are respectively added into raw materials of an inner layer and an outer layer of the polyethylene water supply pipe as reinforcing agents, the effects of physical crosslinking and heterogeneous nucleation are exerted, and the mechanical property of the prepared polyethylene water supply pipe is improved.
2. According to the high-strength polyethylene water supply pipe and the preparation method thereof, epoxy resin with a phenyl ether and double bond structure is prepared through the reaction between 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone and epichlorohydrin, and is crosslinked with high-density polyethylene in an outer layer raw material system under the action of a peroxide crosslinking agent to prepare modified polyethylene, so that the component strength of the outer layer raw material resin is improved, and simultaneously the modified polyethylene is crosslinked and cured with calcium sulfate whiskers modified by aminosiloxane, so that the outer layer system in the polyethylene water supply pipe forms a three-dimensional network structure, and the high-strength polyethylene water supply pipe is obtained.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clearly and completely described, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, high density polyethylene: YGH041, melt Mass Flow Rate (MFR) 0.4g/10min, from China petrochemical Shanghai petrochemical Co., ltd;
zinc oxide: particle size 100nm, from Beijing De Korea island gold technology Co., ltd;
titanate coupling agent from Nanjing Netherlands New Material technology Co;
polyethylene wax: SX-100B is derived from the petrifaction of Yanshan;
calcium sulfate whisker: B6W556, from bokey ecological engineering, inc;
antioxidant 1010, from basf (china) limited;
color master batch: black master, from kunshan color plastic pigment limited.
Example 1: the preparation method of the high-strength polyethylene water supply pipe comprises the following steps:
s1, preparation of inner layer raw materials:
mixing 46g of zinc oxide, 8g of titanate coupling agent and 4g of dispersing agent polyethylene wax in a high-speed stirrer, stirring at 115 ℃ for 5min at high speed, and drying in vacuum for 100min; mixing with 920g of high-density polyethylene, stirring uniformly, extruding and granulating in a double-screw extruder, wherein the extrusion temperature is 170-210 ℃, and drying for 24 hours;
s2, preparing an outer layer raw material:
(1) Preparation of epoxy resin:
taking 0.30mol of 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone and 2.85mol of epichlorohydrin, adding n-butanol and 1.77g of benzyl trimethyl ammonium bromide, mixing, heating to 100 ℃, reacting for 3 hours, and steaming; the temperature of the system is reduced to 70 ℃, 112mL of 30% sodium hydroxide solution is added for reaction for 4 hours; adding distilled water and toluene, stirring, standing for layering, taking a resin layer, washing to be neutral, steaming in a rotary mode, adding ethyl acetate, taking a liquid phase, and drying to constant weight to obtain epoxy resin;
(2) Preparation of modified polyethylene:
vacuum drying high-density polyethylene at 70 ℃ for 24 hours for dehydration; taking 2g of cross-linking agent benzoyl peroxide and 1g of degradation inhibitor tetramethylthiuram disulfide, adding 100g of acetone for dissolution, mixing with 1000g of high-density polyethylene and 50g of epoxy resin, and uniformly mixing in a high-speed stirrer after the acetone volatilizes; extruding and granulating in a double-screw extruder at 170-220 deg.c and drying for 24 hr to obtain modified polyethylene;
(3) Preparation of modified calcium sulfate whisker:
mixing 3.0-gKH, 270g of absolute ethyl alcohol and 30g of distilled water, adding 100g of calcium sulfate whisker, stirring, and carrying out forced air drying at 100 ℃ for 4 hours to obtain modified calcium sulfate whisker;
(4) Preparation of outer layer raw materials:
taking 900g of modified polyethylene, 8g of antioxidant 1010, 20g of color master batch and 90g of modified calcium sulfate whisker, extruding and granulating in a double-screw extruder, and drying for 24 hours at 165-200 ℃ to obtain an outer layer raw material;
s3, preparing a polyethylene water supply pipe:
taking inner layer raw materials and outer layer raw materials, carrying out double-layer co-extrusion, wherein the temperature of a heating zone is 170-225 ℃, the temperature of inner layer extrusion is 170-220 ℃, the temperature of outer layer extrusion is 175-230 ℃, and forming an inner layer and an outer layer to obtain a polyethylene water supply pipe with the nominal outer diameter De of 140mm, the wall thickness is 4.3mm, and the thickness ratio of the inner layer to the outer layer is 1:1.2.
Example 2: the preparation method of the high-strength polyethylene water supply pipe comprises the following steps:
s1, preparation of inner layer raw materials:
47.5g of zinc oxide, 9.0g of titanate coupling agent and 4.5g of dispersing agent polyethylene wax are placed in a high-speed stirrer to be mixed, and are placed at 120 ℃ to be stirred for 8min at high speed, and are dried for 120min in vacuum; mixing with 950g of high-density polyethylene, stirring uniformly, extruding and granulating in a double-screw extruder, wherein the extrusion temperature is 170-210 ℃, and drying for 24 hours;
s2, preparing an outer layer raw material:
(1) Preparation of epoxy resin:
taking 0.30mol of 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone and 2.85mol of epichlorohydrin, adding n-butanol and 2.13g of benzyl trimethyl ammonium bromide, mixing, heating to 110 ℃, reacting for 3.5 hours, and steaming; the temperature of the system is reduced to 72 ℃, 112mL of 32% sodium hydroxide solution is added for reaction for 5 hours; adding distilled water and toluene, stirring, standing for layering, taking a resin layer, washing to be neutral, steaming in a rotary mode, adding ethyl acetate, taking a liquid phase, and drying to constant weight to obtain epoxy resin;
(2) Preparation of modified polyethylene:
vacuum drying high-density polyethylene at 70 ℃ for 24 hours for dehydration; taking 3.5g of cross-linking agent benzoyl peroxide and 1.5g of degradation inhibitor tetramethylthiuram disulfide, adding 110g of acetone for dissolution, mixing with 1000g of high-density polyethylene and 85g of epoxy resin, and uniformly mixing in a high-speed stirrer after the acetone volatilizes; extruding and granulating in a double-screw extruder at 170-220 deg.c and drying for 24 hr to obtain modified polyethylene;
(3) Preparation of modified calcium sulfate whisker:
mixing 4.0-gKH g of absolute ethyl alcohol, 360g of distilled water and 40g of distilled water, adding 100g of calcium sulfate whisker, stirring, and carrying out forced air drying at 100 ℃ for 4 hours to obtain modified calcium sulfate whisker;
(4) Preparation of outer layer raw materials:
taking 950g of modified polyethylene, 9g of antioxidant 1010, 25g of color master batch and 95g of modified calcium sulfate whisker, extruding and granulating in a double-screw extruder, and drying for 24 hours at 165-200 ℃ to obtain an outer layer raw material;
s3, preparing a polyethylene water supply pipe:
taking inner layer raw materials and outer layer raw materials, carrying out double-layer co-extrusion, wherein the temperature of a heating zone is 170-225 ℃, the temperature of inner layer extrusion is 170-220 ℃, the temperature of outer layer extrusion is 175-230 ℃, and forming an inner layer and an outer layer to obtain a polyethylene water supply pipe with the nominal outer diameter De of 140mm, the wall thickness is 4.3mm, and the thickness ratio of the inner layer to the outer layer is 1:1.2.
Example 3: the preparation method of the high-strength polyethylene water supply pipe comprises the following steps:
s1, preparation of inner layer raw materials:
49g of zinc oxide, 10g of titanate coupling agent and 5g of dispersing agent polyethylene wax are placed in a high-speed stirrer to be mixed, placed at 125 ℃ to be stirred for 10min at high speed, and dried in vacuum for 150min; mixing with 980g high-density polyethylene, stirring uniformly, extruding and granulating in a double-screw extruder, wherein the extrusion temperature is 170-210 ℃, and drying for 24 hours;
s2, preparing an outer layer raw material:
(1) Preparation of epoxy resin:
taking 0.30mol of 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone and 2.85mol of epichlorohydrin, adding n-butanol and 2.49g of benzyl trimethyl ammonium bromide, mixing, heating to 120 ℃, reacting for 4 hours, and steaming; the temperature of the system is reduced to 75 ℃, 110mL of 35% sodium hydroxide solution is added for reaction for 6 hours; adding distilled water and toluene, stirring, standing for layering, taking a resin layer, washing to be neutral, steaming in a rotary mode, adding ethyl acetate, taking a liquid phase, and drying to constant weight to obtain epoxy resin;
(2) Preparation of modified polyethylene:
vacuum drying high-density polyethylene at 70 ℃ for 24 hours for dehydration; taking 5g of cross-linking agent benzoyl peroxide and 2g of degradation inhibitor tetramethylthiuram disulfide, adding 120g of acetone for dissolution, mixing with 1000g of high-density polyethylene and 120g of epoxy resin, and uniformly mixing in a high-speed stirrer after the acetone volatilizes; extruding and granulating in a double-screw extruder at 170-220 deg.c and drying for 24 hr to obtain modified polyethylene;
(3) Preparation of modified calcium sulfate whisker:
mixing 5.0-gKH g of absolute ethyl alcohol, 450g of distilled water and 50g of distilled water, adding 100g of calcium sulfate whisker, stirring, and carrying out forced air drying at 100 ℃ for 4 hours to obtain modified calcium sulfate whisker;
(4) Preparation of outer layer raw materials:
taking 1000g of modified polyethylene, 10g of antioxidant 1010, 30g of color master batch and 100g of modified calcium sulfate whisker, extruding and granulating in a double-screw extruder, and drying for 24 hours at 165-200 ℃ to obtain an outer layer raw material;
s3, preparing a polyethylene water supply pipe:
taking inner layer raw materials and outer layer raw materials, carrying out double-layer co-extrusion, wherein the temperature of a heating zone is 170-225 ℃, the temperature of inner layer extrusion is 170-220 ℃, the temperature of outer layer extrusion is 175-230 ℃, and forming an inner layer and an outer layer to obtain a polyethylene water supply pipe with the nominal outer diameter De of 140mm, the wall thickness is 4.3mm, and the thickness ratio of the inner layer to the outer layer is 1:1.2.
Comparative example 1: a preparation method of a high-strength polyethylene water supply pipe,
s2, preparing an outer layer raw material:
(1) Preparation of epoxy resin:
taking 0.30mol of bisphenol S and 2.85mol of epichlorohydrin, adding n-butanol and 1.34g of benzyl trimethyl ammonium bromide, mixing, heating to 100 ℃, reacting for 3 hours, and steaming; the temperature of the system is reduced to 70 ℃, 112mL of 30% sodium hydroxide solution is added for reaction for 4 hours; adding distilled water and toluene, stirring, standing for layering, taking a resin layer, washing to be neutral, steaming in a rotary mode, adding ethyl acetate, taking a liquid phase, and drying to constant weight to obtain epoxy resin;
(2) Preparation of modified polyethylene:
vacuum drying high-density polyethylene at 70 ℃ for 24 hours for dehydration; taking 2g of cross-linking agent benzoyl peroxide and 1g of degradation inhibitor tetramethylthiuram disulfide, adding 100g of acetone for dissolution, mixing with 1000g of high-density polyethylene and 50g of epoxy resin, and uniformly mixing in a high-speed stirrer after the acetone volatilizes; extruding and granulating in a double-screw extruder at 170-220 deg.c and drying for 24 hr to obtain modified polyethylene;
(3) Preparation of modified calcium sulfate whisker:
mixing 3.0-gKH, 270g of absolute ethyl alcohol and 30g of distilled water, adding 100g of calcium sulfate whisker, stirring, and carrying out forced air drying at 100 ℃ for 4 hours to obtain modified calcium sulfate whisker;
(4) Preparation of outer layer raw materials:
taking 900g of modified polyethylene, 8g of antioxidant 1010, 20g of color master batch and 90g of modified calcium sulfate whisker, extruding and granulating in a double-screw extruder, and drying for 24 hours at 165-200 ℃ to obtain an outer layer raw material;
steps S1 and S3 were the same as in example 1 to obtain a polyethylene water feed pipe.
Comparative example 2: a preparation method of a high-strength polyethylene water supply pipe,
s2, preparing an outer layer raw material:
(1) Preparation of modified polyethylene:
vacuum drying high-density polyethylene at 70 ℃ for 24 hours for dehydration; 2g of cross-linking agent benzoyl peroxide and 1g of degradation inhibitor tetramethylthiuram disulfide are taken, 100g of acetone is added for dissolution, and mixed with 1000g of high-density polyethylene and 50g of epoxy resin (E-44, the epoxy value is 0.42 g/100g and derived from Baling petrochemical industry), and after the acetone volatilizes, the mixture is uniformly mixed in a high-speed stirrer; extruding and granulating in a double-screw extruder at 170-220 deg.c and drying for 24 hr to obtain modified polyethylene;
(2) Preparation of modified calcium sulfate whisker:
mixing 3.0-gKH, 270g of absolute ethyl alcohol and 30g of distilled water, adding 100g of calcium sulfate whisker, stirring, and carrying out forced air drying at 100 ℃ for 4 hours to obtain modified calcium sulfate whisker;
(3) Preparation of outer layer raw materials:
taking 900g of modified polyethylene, 8g of antioxidant 1010, 20g of color master batch and 90g of modified calcium sulfate whisker, extruding and granulating in a double-screw extruder, and drying for 24 hours at 165-200 ℃ to obtain an outer layer raw material;
steps S1 and S3 were the same as in example 1 to obtain a polyethylene water feed pipe.
Comparative example 3: a preparation method of a high-strength polyethylene water supply pipe,
s2, preparing an outer layer raw material:
(1) Preparation of modified calcium sulfate whisker:
mixing 3.0-gKH, 270g of absolute ethyl alcohol and 30g of distilled water, adding 100g of calcium sulfate whisker, stirring, and carrying out forced air drying at 100 ℃ for 4 hours to obtain modified calcium sulfate whisker;
(2) Preparation of outer layer raw materials:
taking 900g of high-density polyethylene, 8g of antioxidant 1010, 20g of color master batch and 90g of modified calcium sulfate whisker, extruding and granulating in a double-screw extruder, and drying for 24 hours at 165-200 ℃ to obtain an outer layer raw material;
steps S1 and S3 were the same as in example 1 to obtain a polyethylene water feed pipe.
Comparative example 4: the preparation method of the high-strength polyethylene water supply pipe comprises the following steps:
s1, preparation of inner layer raw materials:
mixing 46g of zinc oxide with 920g of high-density polyethylene, uniformly stirring, extruding and granulating in a double-screw extruder, wherein the extrusion temperature is 170-210 ℃, and drying for 24 hours;
s2, preparing an outer layer raw material:
taking 900g of high-density polyethylene, 8g of antioxidant 1010, 20g of color master batch and 90g of calcium sulfate whisker, extruding and granulating in a double-screw extruder, and drying for 24 hours at 165-200 ℃ to obtain an outer layer raw material;
step S3 was the same as in example 1 to obtain a polyethylene water feed pipe.
Experiment: taking the polyethylene water supply pipes obtained in examples 1-3 and comparative examples 1-4, preparing samples, respectively detecting the performances of the samples and recording the detection results:
tensile properties: using GB/T1040-2018 as a reference standard, adopting an electronic tensile testing machine to test the tensile property of a sample, wherein the size of the sample is 110mm multiplied by 25mm multiplied by 4.0mm, and the tensile rate is 50mm/min;
bending properties: using GB/T9341-2008 as a reference standard, adopting a bending tester to test the bending performance of a sample, wherein the sample size is 80mm multiplied by 10mm multiplied by 4.0mm, the radius of a pressure head is 5.0mm, the radius of a support is 5.0mm, and the test speed is 2mm/min;
impact properties: the impact property of the test sample is tested by using a impact tester by taking GB/T1043-2008 as a reference standard, the test sample size is 80mm multiplied by 10mm multiplied by 4.0mm, and the radius of the bottom of the notch is 1.0mm.
From the data in the above table, the following conclusions can be clearly drawn:
the polyethylene water supply pipes obtained in examples 1 to 3 were compared with the polyethylene water supply pipes obtained in comparative examples 1 to 4, and it was found that the results of the detection,
the polyethylene water supply pipes obtained in examples 1 to 3 have higher tensile strength, impact strength and bending strength data than the comparative examples, which fully demonstrates that the present invention achieves an improvement in the strength of the produced polyethylene water supply pipes.
In comparison with example 1, the 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone was replaced with bisphenol S in an equimolar amount, the epoxy resin was replaced with E-44 in comparative example 2, the component epoxy resin was not added in comparative example 3, the high density polyethylene and the filler were not modified in comparative example 4, and the tensile strength, impact strength and flexural strength data were all reduced; it is known that the arrangement of the polyethylene water supply pipe component and the process thereof can promote the improvement of the strength.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of a high-strength polyethylene water supply pipe is characterized by comprising the following steps: the method comprises the following steps:
taking high-density polyethylene, zinc oxide and a processing aid as inner layer raw materials, taking modified polyethylene, modified calcium sulfate whisker and the processing aid as outer layer raw materials, and performing double-layer co-extrusion to form an inner layer and an outer layer to obtain a polyethylene water supply pipe;
the modified polyethylene in the outer layer raw material is prepared by crosslinking high-density polyethylene with epoxy resin with unsaturated double bonds under the action of a peroxide crosslinking agent, and the modified calcium sulfate whisker is prepared by modifying calcium sulfate whisker by an amino coupling agent;
the outer layer raw material is prepared by the following process:
step (1): taking 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone and epichlorohydrin, adding n-butanol and benzyl trimethyl ammonium bromide, mixing, heating to 100-120 ℃, reacting for 3-4 h, and rotary steaming; the temperature of the system is reduced to 70-75 ℃, and sodium hydroxide solution is added for reaction for 4-6 hours to obtain epoxy resin;
step (2): adding peroxide cross-linking agent and degradation inhibitor into acetone for dissolution, mixing with high-density polyethylene and epoxy resin, and uniformly mixing in a high-speed stirrer after the acetone volatilizes; extruding and granulating in a double-screw extruder at 170-220 deg.c and drying for 24 hr to obtain modified polyethylene;
step (3): mixing an amino coupling agent, absolute ethyl alcohol and distilled water, adding calcium sulfate whiskers, stirring, and carrying out forced air drying at 100 ℃ for 4 hours to obtain modified calcium sulfate whiskers;
step (4): mixing the modified polyethylene, the antioxidant, the color masterbatch and the modified calcium sulfate whisker, extruding and granulating in a double-screw extruder, wherein the extruding temperature is 165-200 ℃, and drying for 24 hours to obtain the outer layer raw material.
2. The method for preparing a high-strength polyethylene water supply pipe according to claim 1, wherein: the processing aid is a mixture of two or more of a coupling agent, a dispersing agent, color master batches and an antioxidant.
3. The method for preparing a high-strength polyethylene water supply pipe according to claim 2, wherein: the inner layer raw material comprises the following components in parts by mass: 92-98 parts of high-density polyethylene, 4.6-4.9 parts of zinc oxide, 0.8-1.0 parts of coupling agent and 0.4-0.5 part of dispersing agent.
4. The method for preparing a high-strength polyethylene water supply pipe according to claim 2, wherein: the outer layer raw materials comprise the following components in parts by mass: 90 to 100 parts of modified polyethylene, 9 to 10 parts of modified calcium sulfate whisker, 0.8 to 1.0 part of antioxidant and 2 to 3 parts of color master batch.
5. A method of producing a high strength polyethylene water feed pipe according to claim 3, wherein: the inner layer raw material is prepared by the following process:
mixing zinc oxide, a coupling agent and a dispersing agent in a high-speed stirrer, stirring at a high speed at 115-125 ℃ for 5-10 min, and vacuum drying for 100-150 min;
mixing with high-density polyethylene, stirring, extruding in a double-screw extruder, granulating at 170-210 deg.C, and drying for 24 hr.
6. The method for preparing a high-strength polyethylene water supply pipe according to claim 1, wherein: in the step (1), the molar ratio of 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone to epichlorohydrin is 1 (9.5-10.5);
the molar ratio of 3,3 '-diallyl-4, 4' -dihydroxydiphenyl sulfone to sodium hydroxide is 1 (2.8-3.2).
7. The method for preparing a high-strength polyethylene water supply pipe according to claim 1, wherein: in the step (2), the mass ratio of the high-density polyethylene to the epoxy resin to the acetone to the degradation inhibitor tetramethylthiuram disulfide to the cross-linking agent benzoyl peroxide is 100 (5-12)/(10-12)/(0.1-0.2)/(0.2-0.5).
8. The method for preparing a high-strength polyethylene water supply pipe according to claim 1, wherein: in the step (3), the amino coupling agent is KH-540 or KH-550; the mass ratio of the calcium sulfate whisker and the amino coupling agent is 100 (3.0-5.0).
9. A high strength polyethylene water feed pipe made according to the method of any one of claims 1-8.
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| JP4259834B2 (en) * | 2002-09-19 | 2009-04-30 | 日本化薬株式会社 | Epoxy resin, epoxy resin composition and cured product thereof |
| CN107849221A (en) * | 2015-08-07 | 2018-03-27 | 日本化药株式会社 | Epoxy resin, modified epoxy, epoxy resin component and its hardening thing |
| CN109111626A (en) * | 2018-07-30 | 2019-01-01 | 江苏星河集团有限公司 | A kind of Antibacterial flame retardant plastic pipeline |
| CN109627545A (en) * | 2018-11-30 | 2019-04-16 | 盐城市瑞通塑胶有限公司 | A kind of anti-high-pressure anticorrosion HDPE double-wall corrugated pipe and preparation method thereof |
| CN109517251A (en) * | 2018-11-30 | 2019-03-26 | 江苏洁润管业有限公司 | A kind of High-strength antibacterial type tubing |
| CN111022786B (en) * | 2019-12-30 | 2021-06-15 | 安徽杰蓝特新材料有限公司 | Glass fiber reinforced PE water supply pipe and preparation method thereof |
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