CN113321823A - Polyethylene red phosphorus flame-retardant master batch and preparation method and application thereof - Google Patents
Polyethylene red phosphorus flame-retardant master batch and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of polyethylene red phosphorus flame-retardant master batches, and particularly relates to a polyethylene red phosphorus flame-retardant master batch as well as a preparation method and application thereof. The polyethylene red phosphorus flame-retardant master batch is prepared by selecting the pipeline-grade polyethylene as a base body, grinding the pipeline-grade polyethylene into powder, and is beneficial to uniform mixing with components such as cladding red phosphorus, and the like. Meanwhile, maleic anhydride and polysiloxane bifunctional modified polyethylene are used as compatilizers, so that the dispersibility of the flame retardant is improved, and the appearance of the processed pipe can be improved. The carbon nano tube is used as a synergistic flame retardant, so that the surface resistance of the mining tube can be reduced while the flame retardant effect is improved.
Description
Technical Field
The invention relates to the field of polyethylene red phosphorus flame-retardant master batches, and particularly relates to a polyethylene red phosphorus flame-retardant master batch as well as a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The polyethylene for underground coal mine and the composite pipeline thereof need to meet the requirements of MT181 on flame retardance and static resistance. The mining polyethylene pipe commonly uses decabromodiphenyl ether, nitrogen and phosphorus compound flame retardant, red phosphorus flame retardant and the like as flame retardants, and is matched with conductive carbon black as an antistatic agent, so that the addition amount of the flame retardant and the conductive agent in polyethylene exceeds 30%, and the pipeline has high brittleness and poor pressure resistance. The red phosphorus flame retardant is most widely used in mining polyethylene pipelines due to high efficiency and small addition amount.
The flame-retardant and antistatic polyethylene material has the problems of flying powder, easy ignition and the like in the production process due to the addition of materials such as conductive carbon black, red phosphorus and the like. Conductive agents such as conductive carbon black are often made into conductive master batches, flame retardants such as red phosphorus are made into flame-retardant master batches, or the flame retardants and the conductive agents are made into flame-retardant antistatic master batches together. The prior art discloses an antistatic polyethylene mining pipe master batch which comprises 90-110 parts of polyethylene, 5-20 parts of metal particles, 5-30 parts of flame retardant, 1-8 parts of stabilizer, 0.5-3 parts of surfactant and 5-20 parts of carbon black. Also discloses an antistatic functional master batch, which mainly comprises the following components in parts by mass: 20-50 parts of LLDPE with the melt mass flow rate of more than 10g/10min, 2-10 parts of EVA, 1-8 parts of POE, 5-12 parts of conductive carbon black, 1-6 parts of coated red phosphorus, 0.1-4 parts of processing aid and 2-10 parts of compatilizer.
However, the inventor researches and discovers that in the process of preparing the master batch, an internal mixer or a twin-screw is mainly used for mixing the pipeline-grade polyethylene material, in order to achieve a good dispersion effect, a large amount of polyethylene wax or low-molecular auxiliary agent is needed to be used as a dispersing agent in a production formula, and high-fluidity polyethylene is needed to be used as a matrix, so that the mining pipeline prepared by the existing polyethylene antistatic flame-retardant master batch has high brittleness and poor pressure resistance. And the polyethylene with high melt mass flow rate (such as low density polyethylene or linear low density polyethylene with the flow rate of 20-50g/10 min) is selected as a matrix, which is beneficial to preparing high-concentration master batch. However, high flow polyethylene is a non-pipeline grade material and does not have long term hydrostatic resistance.
Disclosure of Invention
In order to solve the problems of large brittleness, poor static hydraulic pressure resistance and more added auxiliary materials of the existing mining pipe with a low-density polyethylene or linear low-density polyethylene matrix, the invention develops a new method, provides a polyethylene red phosphorus flame-retardant master batch, selects the pipeline-grade polyethylene as the matrix, is beneficial to the uniform mixing with components such as coating red phosphorus and the like by grinding the pipeline-grade polyethylene into powder, and cannot generate adverse effect on an applied pipeline because the matrix used by the flame-retardant master batch is also pipeline-grade polyethylene (high density), thereby improving the pressure resistance of the flame-retardant master batch used for the mining pipeline. Meanwhile, maleic anhydride and polysiloxane bifunctional modified polyethylene are used as compatilizers, so that the dispersibility of the flame retardant is improved, and the appearance of the processed pipe can be improved. The carbon nano tube is used as a synergistic flame retardant, so that the surface resistance of the mining tube can be reduced while the flame retardant effect is improved.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the present invention, a polyethylene red phosphorus flame retardant masterbatch is provided, comprising: coating red phosphorus, carbon nano tubes, pipeline-grade polyethylene, bifunctional modified polyethylene and an auxiliary agent.
In a second aspect of the present invention, a method for preparing a polyethylene red phosphorus flame retardant masterbatch is provided, which comprises: uniformly mixing the coated red phosphorus, the carbon nano tube, the pipeline-grade polyethylene, the bifunctional modified polyethylene and the auxiliary agent, then carrying out melt blending on the blend at the temperature of 170-200 ℃ by using a double-screw extruder, and granulating to obtain the polyethylene red phosphorus flame-retardant master batch.
In a third aspect of the invention, there is provided a mining pipe comprising carbon black, the polyethylene red phosphorus flame retardant masterbatch of claim, and pipeline grade polyethylene.
The invention provides a preparation method of a mining pipe, which comprises the following steps: uniformly mixing carbon black, polyethylene red phosphorus flame-retardant master batch and pipeline-grade polyethylene, granulating at 180-200 ℃ by using an extruder to obtain the flame-retardant antistatic special material, and extruding the pipe material by using pipeline processing equipment.
In a fifth aspect of the invention, a secondary pipe network system and/or a hot water system of a hot spring pipeline and/or an air conditioner water inlet and return heat insulation pipeline system and/or an indoor and outdoor water supply pipe network and/or low-temperature radiation heating is provided, wherein the secondary pipe network system and/or the hot water system of the hot spring pipeline and/or the air conditioner water inlet and return heat insulation pipeline system comprises a polyethylene red phosphorus flame-retardant master batch and/or a mining pipe.
One or more technical schemes of the invention have the following beneficial effects:
1) in the prior art, polyethylene with high melt mass flow rate (such as low density polyethylene or linear low density polyethylene with the flow rate of 20-50g/10 min) is generally selected as a matrix, which is beneficial to preparing high-concentration master batch. However, high flow polyethylene is a non-pipeline grade material and does not have long term hydrostatic resistance. The invention selects the pipeline-grade polyethylene as the matrix, and the pipeline-grade polyethylene is ground into powder, so that the uniform mixing of the pipeline-grade polyethylene and the components for coating red phosphorus and the like is facilitated.
However, the conventional pipeline-grade polyethylene has low melt flow rate and poor fluidity, so that the pipeline material is ground into powder, the mixing in the production process of the red phosphorus master batch is facilitated, the ignition problem caused by red phosphorus aggregation in the production process is avoided, and meanwhile, the maleic anhydride and polysiloxane bifunctional modified polyethylene is adopted to improve the dispersibility of the red phosphorus and reduce the viscosity of the melt during processing, so that the red phosphorus master batch can be industrially produced, and meanwhile, the pipeline has excellent pressure resistance.
2) Compared with the prior art that low molecular dispersing agents such as polyethylene wax, engine oil, stearate and the like are adopted for the pipeline-grade polyethylene material, the invention adopts the polyethylene which is modified by the maleic anhydride and the polysiloxane in a bifunctional way as the dispersing agent. Compared with the prior art which uses low molecular dispersing agents such as polyethylene wax and oil, the flame-retardant master batch provided by the invention is applied to polyethylene double-resistant materials (pipeline-grade polyethylene substrates), and the appearance of the pipe and the pressure bearing of the pipeline cannot be influenced due to the precipitation of the low molecular dispersing agents; compared with the prior art that silicone oil and polysiloxane are used as dispersing agents, the organic peroxide is adopted to initiate polysiloxane and polyethylene to form block reaction, so that polysiloxane is connected to a polyethylene molecular chain, and the problems of precipitation, uneven dispersion and the like caused by poor compatibility can be avoided while the effects of improving dispersion and reducing surface tension are achieved; compared with the polar monofunctional grafted dispersing agent in the prior art, such as maleic anhydride grafted polyolefin and acrylic acid grafted modified polyolefin, the grafted maleic anhydride interacts with melamine resin coating the surface of red phosphorus and polar groups of carbon nanotubes, so that the dispersion of the red phosphorus and the carbon nanotubes in a matrix can be promoted, and polysiloxane grafted on polyethylene molecules can reduce the surface tension of a melt and reduce the viscosity of the melt extruded from a pipe so as to improve the brightness of the extruded appearance of the pipe.
3) The inventor researches and discovers that the carbon nano tube has a synergistic flame retardant effect on red phosphorus. Meanwhile, the carbon nano tube has excellent conductive capability, so that the addition of the red phosphorus flame-retardant master batch can reduce the surface resistance of the mining tube and improve the antistatic effect of the pipeline, thereby improving the application safety of the mining pipeline.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The inventor researches and discovers that in the process of preparing the master batch, an internal mixer or a twin-screw is mainly used for mixing the pipeline-grade polyethylene material, in order to achieve a good dispersion effect, a large amount of polyethylene wax or low-molecular auxiliary agent is needed to be used as a dispersing agent in a production formula, and high-fluidity polyethylene is needed to be used as a matrix, so that the mining pipeline prepared by the existing polyethylene antistatic flame-retardant master batch has high brittleness and poor pressure resistance. And the polyethylene with high melt mass flow rate (such as low density polyethylene or linear low density polyethylene with the flow rate of 20-50g/10 min) is selected as a matrix, which is beneficial to preparing high-concentration master batch. However, high flow polyethylene is a non-pipeline grade material and does not have long term hydrostatic resistance. In order to solve the problems, the invention provides a polyethylene red phosphorus flame-retardant master batch,
specifically, the invention is realized by the following technical scheme:
in a first aspect of the present invention, a polyethylene red phosphorus flame retardant masterbatch is provided, comprising: coating red phosphorus, carbon nano tubes, pipeline-grade polyethylene, bifunctional modified polyethylene and an auxiliary agent.
Pipeline polyethylene is used as a matrix, so that the pressure resistance of the master batch for the mining pipe is improved. In the prior art, polyethylene with high melt mass flow rate (such as low density polyethylene or linear low density polyethylene with the flow rate of 20-50g/10 min) is generally selected as a matrix, which is beneficial to preparing high-concentration master batch. However, high flow polyethylene is a non-pipeline grade material and does not have long term hydrostatic resistance. The invention selects the pipeline-grade polyethylene as the matrix, and the pipeline-grade polyethylene is ground into powder, so that the uniform mixing of the pipeline-grade polyethylene and the components for coating red phosphorus and the like is facilitated.
In one or more embodiments of the invention, by weight, 40-50 parts of coated red phosphorus, 5-10 parts of carbon nanotubes, 40-50 parts of pipeline-grade polyethylene, 3-7 parts of bifunctional modified polyethylene and 0.3-2 parts of an auxiliary agent. When the master batch is prepared into a pipe, the average flame combustion time is 0.53-1.2s and the surface resistance is less than 2.8 x 10 when the content is the value5Omega, the hydrostatic pressure at 20 ℃ exceeds 300h, the appearance is bright, and the comprehensive performance is better. And the flame retardant used in the invention is a red phosphorus flame retardant, so that the flame retardant efficiency is high and the addition amount is low.
In order to further improve the performance of the pipe, the polyethylene red phosphorus flame-retardant master batch comprises, by weight, 40-45 parts of coated red phosphorus, 7-10 parts of carbon nano tubes, 40-45 parts of pipeline-grade polyethylene, 4.7-7 parts of bifunctional modified polyethylene and 0.3-1 part of auxiliary agent, wherein the polyethylene red phosphorus flame-retardant master batch prepared by the components can ensure that the average flame combustion time of the pipe is 0.53-0.81s, and the surface resistance is less than 6.4 x 104Omega, the hydrostatic pressure at 20 ℃ exceeds 300h, the appearance is bright, and the comprehensive performance is further improved.
Experiments show that when 45 parts of red phosphorus, 7 parts of carbon nano tubes, 40 parts of pipeline-grade polyethylene, 47 parts of bifunctional modified polyethylene and 1 part of auxiliary agent are coated by weight, the polyethylene red phosphorus flame-retardant master batch prepared by the components can ensure that the average flame combustion time of the pipe is 0.53s, and the surface resistance is 1.3 to 104Omega, the hydrostatic pressure at 20 ℃ exceeds 300h, the appearance is bright, and the comprehensive performance is optimal.
If the composition or the content of the components is changed, the property of the polyethylene red phosphorus flame-retardant master batch can be influenced, and the performance of a pipeline containing the polyethylene red phosphorus flame-retardant master batch is further influenced, for example, the average flame combustion time is prolonged, the surface resistance is increased, the hydrostatic pressure time at 20 ℃ is short, the pipeline is damaged, the surface glossiness is low, even pockmarks exist, and the use safety is influenced.
Meanwhile, experimental research finds that in the polyethylene red phosphorus flame-retardant master batch taking pipeline-grade polyethylene as a matrix, the carbon nano tube and the bifunctional modified polyethylene also have a synergistic effect, and the specific expression is as follows: meanwhile, the pipe made of the polyethylene red phosphorus flame-retardant master batch of the carbon nano tube and the bifunctional modified polyethylene does not have the advantage that the hydrostatic pressure difference at 20 ℃ is larger than that of the pipe made of the polyethylene red phosphorus flame-retardant master batch of the carbon nano tube or the bifunctional modified polyethylene, and the pipe is damaged only within 10.6 hours. Meanwhile, the average flame combustion time of the pipe prepared by using the polyethylene red phosphorus flame-retardant master batch of the carbon nano tube and the bifunctional modified polyethylene is obviously shortened compared with that of the pipe prepared by singly using the polyethylene red phosphorus flame-retardant master batch of the carbon nano tube or the bifunctional modified polyethylene, and the flame retardant property is more excellent.
In one or more embodiments of the present invention, the coated red phosphorus is melamine resin coated red phosphorus, the content of red phosphorus in the coated red phosphorus is greater than or equal to 80%, and the particle size of the coated red phosphorus is 500-. In some embodiments of the invention, the coated red phosphorus is commercially available from Henan Corey New flame retardant materials, Inc. or from Ringning civilian chemical industries.
The carbon nano tube is used as a synergistic flame retardant, so that the surface resistance of the mining tube can be reduced while the flame retardant effect is improved. Through the research of the inventor, the carbon nano tube has a synergistic flame retardant effect on red phosphorus. Meanwhile, the carbon nano tube has excellent conductive capability, so that the addition of the red phosphorus flame-retardant master batch can reduce the surface resistance of the mining tube and improve the antistatic effect of the pipeline, thereby improving the application safety of the mining pipeline. In some embodiments, the carbon nanotubes are selected from at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes.
Preferably, the pipeline-grade polyethylene is high-density polyethylene, and is selected from at least one of PE 80-grade polyethylene, PE 100-grade polyethylene, type I PE-RT and type II PE-RT;
the grade of the PE pipeline raw material is divided into PE63 grade PE80 grade and PE100 grade, relatively speaking, the PE100 grade has the best pressure-bearing performance and the worst flexibility, the PE63 has the worst pressure-bearing performance and the best flexibility, and the PE80 is between the two grades.
The PE-RT I-shaped pipe is prepared by polymerizing medium-density polyethylene (MDPE) and octene, and is limited to be used in a low-temperature pipeline system below 70 ℃. The PE-RT I-shaped pipe is generally applied to indoor and outdoor water supply pipe networks and low-temperature ground radiation heating.
The raw material used by the PE-RT II type pipe is French Doudal (brand number XRT70), which is a high molecular material formed by copolymerizing High Density Polyethylene (HDPE) and hexene or butene. The PE-RT II type pipe is suitable for high-temperature hot water pipeline systems, and the normal use temperature is 20-95 ℃. The PE-RT II type pipe is generally applied to urban central heating secondary pipe network systems, hot spring pipeline hot water systems, air conditioner water inlet and return heat preservation pipeline systems and the like.
Preferably, the bifunctional modified polyethylene is polysiloxane, maleic anhydride modified polyethylene.
The polyethylene modified by maleic anhydride and polysiloxane is used as a compatilizer, so that the dispersibility of the flame retardant is improved, and the appearance of the processed pipe can be improved. Compared with the prior art that low molecular dispersing agents such as polyethylene wax, engine oil, stearate and the like are adopted, the invention adopts the maleic anhydride and polysiloxane bifunctional modified polyethylene as the dispersing agent. Compared with the prior art which uses low molecular dispersing agents such as polyethylene wax and oil, the flame-retardant master batch provided by the invention is applied to polyethylene double-resistant materials, and the appearance of the pipe and the pressure bearing of the pipeline cannot be influenced due to the precipitation of the low molecular dispersing agents; compared with the prior art that silicone oil and polysiloxane are used as dispersing agents, the organic peroxide is adopted to initiate polysiloxane and polyethylene to form block reaction, so that polysiloxane is connected to a polyethylene molecular chain, and the problems of precipitation, uneven dispersion and the like caused by poor compatibility can be avoided while the effects of improving dispersion and reducing surface tension are achieved; compared with the polar monofunctional grafted dispersing agent in the prior art, such as maleic anhydride grafted polyolefin and acrylic acid grafted modified polyolefin, the grafted maleic anhydride interacts with melamine resin coating the surface of red phosphorus and polar groups of carbon nanotubes, so that the dispersion of the red phosphorus and the carbon nanotubes in a matrix can be promoted, and polysiloxane grafted on polyethylene molecules can reduce the surface tension of a melt and reduce the viscosity of the melt extruded from a pipe so as to improve the brightness of the extruded appearance of the pipe.
Preferably, the auxiliary agent is at least one of an antioxidant and a light stabilizer, and the antioxidant comprises: JYANOX-1010, B225, B215.
In one or more embodiments of the invention, the bifunctional modified polyethylene dispersant is prepared by grafting 92-97 parts of polyethylene with melt mass flow rate of 5-50g/10min, 2-5 parts of polysiloxane, 1-3 parts of maleic anhydride and 0.02-0.3 part of organic peroxide initiator through a double-screw reaction, wherein the temperature of the grafting reaction is 180-250 ℃, and the rotation speed of the screw is 300-500 rpm.
Compared with the polar monofunctional grafted dispersing agent in the prior art, such as maleic anhydride grafted polyolefin and acrylic acid grafted modified polyolefin, the grafted maleic anhydride interacts with melamine resin coating the surface of red phosphorus and polar groups of carbon nanotubes, so that the dispersion of the red phosphorus and the carbon nanotubes in a matrix can be promoted, and polysiloxane grafted on polyethylene molecules can reduce the surface tension of a melt and reduce the viscosity of the melt extruded from a pipe so as to improve the brightness of the extruded appearance of the pipe.
Preferably, the polysiloxane is selected from at least one of vinyl-terminated polysiloxane 621V 20000, methyl vinyl silicone rubber 110-1 and vinyl-terminated polysiloxane 621V 10000.
Preferably, the organic peroxide initiator is selected from at least one of dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, di-t-butylperoxy diisopropylbenzene.
In a second aspect of the present invention, a method for preparing a polyethylene red phosphorus flame retardant masterbatch is provided, which comprises: uniformly mixing the coated red phosphorus, the carbon nano tube, the pipeline-grade polyethylene, the bifunctional modified polyethylene and the auxiliary agent, then carrying out melt blending on the blend at the temperature of 170-200 ℃ by using a double-screw extruder, and granulating to obtain the polyethylene red phosphorus flame-retardant master batch.
Experimental research shows that the granulation temperature is 200 DEG CThen, the average flame combustion time of the pipe prepared from the polyethylene red phosphorus flame-retardant master batch is 0.53s, and the surface resistance is 1.3 x 104Omega, the hydrostatic pressure at 20 ℃ exceeds 300h, the appearance is bright, and the comprehensive performance is optimal.
In a third aspect of the invention, there is provided a mining pipe comprising carbon black, the polyethylene red phosphorus flame retardant masterbatch of claim, and pipeline grade polyethylene.
In some embodiments, 9 to 12 parts of carbon black, 8 to 10 parts of polyethylene red phosphorus flame retardant masterbatch and 80 to 85 parts of pipeline grade polyethylene by weight.
The invention provides a preparation method of a mining pipe, which comprises the following steps: uniformly mixing carbon black, polyethylene red phosphorus flame-retardant master batch and pipeline-grade polyethylene, granulating at 180-200 ℃ by using an extruder to obtain the flame-retardant antistatic special material, and extruding the pipe material by using pipeline processing equipment.
In a fifth aspect of the invention, a secondary pipe network system and/or a hot water system of a hot spring pipeline and/or an air conditioner water inlet and return heat insulation pipeline system and/or an indoor and outdoor water supply pipe network and/or low-temperature radiation heating is provided, wherein the secondary pipe network system and/or the hot water system of the hot spring pipeline and/or the air conditioner water inlet and return heat insulation pipeline system comprises a polyethylene red phosphorus flame-retardant master batch and/or a mining pipe.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
The polyethylene red phosphorus master batch comprises the following raw materials in parts by weight:
1250-mesh coating red phosphorus (Jining city, Yimin chemical plant) 40 parts; 10 parts of a multi-wall carbon nanotube GT 210 (Shandong Dachang nanometer materials Co., Ltd.); 45 parts of PERT I type pipeline material QHM 22F powder (China petrochemical Qilu petrochemical company); 4.7 parts of bifunctional modified polyethylene dispersant; 0.3 part of antioxidant JYANOX-1010 (Beijing Sujiu chemical Co., Ltd.).
The preparation method of the polyethylene red phosphorus master batch comprises the following specific steps:
preparing a bifunctional modified polyethylene dispersant: polyethylene 8920 (Shaanxi Yangan energy and chemical responsibility Co., Ltd.) with a melt mass flow rate of 20g/10min 93.9 parts, vinyl-terminated polysiloxane 621V 20000 (Jiangxi Lanxing Sihuo organosilicon Co., Ltd.), maleic anhydride (Shandong Zibozixiang Tengda chemical Co., Ltd.) 2 parts, and dicumyl peroxide (Acksutobel peroxide Co., Ltd.) as an organic peroxide initiator 0.1 part are mixed uniformly by a high-speed mixer, and the graft reaction is prepared by a twin-screw reaction at a temperature of 200 ℃ and a screw rotation speed of 420 rpm.
Preparing a red phosphorus master batch: uniformly mixing 40 parts of 1250-mesh coated red phosphorus, 10 parts of multi-walled carbon nanotubes, 45 parts of PERT I-type pipeline material, 4.7 parts of bifunctional modified polyethylene dispersant and 10100.3 parts of antioxidant, and granulating the blend at 170 ℃ by using a double-screw extruder to obtain the polyethylene red phosphorus flame-retardant master batch.
The application of the polyethylene red phosphorus master batch in the mine pipe comprises the following steps:
uniformly mixing 10 parts of conductive carbon black HC-80 (Tianjin Rihua chemical Co., Ltd.), 10 parts of the red phosphorus flame-retardant master batch with the formula and 80 parts of PE 100-grade pipeline material PN049 (Zhongsha petrochemical Co., Ltd.), and granulating by using an extruder at 180 ℃ to obtain the flame-retardant antistatic special material. Then, a 110 x 10mm pipe is extruded on a pipeline processing device, the surface resistance, the flame retardant property and the appearance of the pipe are tested according to MT 558.1, the induced stress is 9MPa, the hydrostatic pressure test is 300h (the standard requirement passes the 100h test) is carried out, and relevant data are shown in Table 1.
Comparative example 1: modification of polyethylene matrix
The polyethylene red phosphorus master batch comprises the following raw materials in parts by weight:
1250-mesh coating red phosphorus (Jining city, Yimin chemical plant) 40 parts; 10 parts of a multi-wall carbon nanotube GT 210 (Shandong Dachang nanometer materials Co., Ltd.); 45 parts of high-fluidity polyethylene powder (number 2650, Tianjin division of China petrochemical industry, Ltd.); 4.7 parts of bifunctional modified polyethylene dispersant; 0.3 part of antioxidant JYANOX-1010 (Beijing Sujiu chemical Co., Ltd.).
The preparation method of the polyethylene red phosphorus master batch comprises the following specific steps:
preparing a bifunctional modified polyethylene dispersant: the same as in example 1.
Preparing a red phosphorus master batch: uniformly mixing 40 parts of 1250-mesh coated red phosphorus, 10 parts of multi-walled carbon nanotubes, 45 parts of high-fluidity polyethylene powder (No. 2650), 4.7 parts of bifunctional modified polyethylene dispersant and 10100.3 parts of antioxidant, and granulating the blend at 170 ℃ by using a double-screw extruder to obtain the polyethylene red phosphorus flame-retardant master batch.
The application of the polyethylene red phosphorus master batch in the mine pipe comprises the following steps: the same as in example 1.
Comparative example 2: without using multi-walled carbon nanotubes
The polyethylene red phosphorus master batch comprises the following raw materials in parts by weight:
1250-mesh coating red phosphorus (Jining city, Yimin chemical plant) 40 parts; 55 parts of PERT I type pipeline material QHM 22F powder (China petrochemical Qilu petrochemical company); 4.7 parts of bifunctional modified polyethylene dispersant; 0.3 part of antioxidant JYANOX-1010 (Beijing Sujiu chemical Co., Ltd.).
The preparation method of the polyethylene red phosphorus master batch comprises the following specific steps:
preparing a bifunctional modified polyethylene dispersant: the same as in example 1.
Preparing a red phosphorus master batch: uniformly mixing 40 parts of 1250-mesh coated red phosphorus, 55 parts of PERT I-type pipeline material, 4.7 parts of bifunctional modified polyethylene dispersant and 10100.3 parts of antioxidant, and granulating the blend at 170 ℃ by using a double-screw extruder to obtain the polyethylene red phosphorus flame-retardant master batch.
The application of the polyethylene red phosphorus master batch in the mine pipe comprises the following steps: as in example 1.
Comparative example 3: the bifunctional modified polyethylene is not used
The polyethylene red phosphorus master batch comprises the following raw materials in parts by weight:
1250-mesh coating red phosphorus (Jining city, Yimin chemical plant) 40 parts; 10 parts of a multi-wall carbon nanotube GT 210 (Shandong Dachang nanometer materials Co., Ltd.); 49.7 parts of PERT I type pipeline material QHM 22F powder (China petrochemical Qilu petrochemical company); 0.3 part of antioxidant JYANOX-1010 (Beijing Sujiu chemical Co., Ltd.).
The preparation method of the polyethylene red phosphorus master batch comprises the following specific steps:
preparing a red phosphorus master batch: uniformly mixing 40 parts of 1250-mesh coated red phosphorus, 10 parts of multi-walled carbon nanotubes, 49.7 parts of PERT I type pipeline material and 10100.3 parts of antioxidant, and granulating the blend at 170 ℃ by using a double-screw extruder to obtain the polyethylene red phosphorus flame-retardant master batch.
The application of the polyethylene red phosphorus master batch in the mine pipe comprises the following steps: as in example 1.
Comparative example 4: bifunctional modified polyethylene and carbon nano tube are not used
The polyethylene red phosphorus master batch comprises the following raw materials in parts by weight:
1250-mesh coating red phosphorus (Jining city, Yimin chemical plant) 40 parts; 59.7 parts of PERT I type pipeline material QHM 22F powder (China petrochemical Qilu petrochemical company); 0.3 part of antioxidant JYANOX-1010 (Beijing Sujiu chemical Co., Ltd.).
The preparation method of the polyethylene red phosphorus master batch comprises the following specific steps:
preparing a red phosphorus master batch: uniformly mixing 40 parts of 1250-mesh coated red phosphorus, 59.7 parts of PERT I-type pipeline material and 10100.3 parts of antioxidant, and granulating the blend at 170 ℃ by using a double-screw extruder to obtain the polyethylene red phosphorus flame-retardant master batch.
The application of the polyethylene red phosphorus master batch in the mine pipe comprises the following steps: as in example 1.
Example 2
The polyethylene red phosphorus master batch comprises the following raw materials in parts by weight:
1250-mesh coating red phosphorus (Jining city, Yimin chemical plant) 45 parts; 7 parts of multi-wall carbon nano-tube FT7000 (Jiangsu Tiannai science and technology Co., Ltd.); 40 parts of PE100 grade pipeline material 100S powder (China Petroleum Jilin petrochemical company); 7 parts of bifunctional modified polyethylene dispersant; 1 part of antioxidant B225 (BASF).
The preparation method of the polyethylene red phosphorus master batch comprises the following specific steps:
preparing a bifunctional modified polyethylene dispersant: 92.95 parts of linear low-density polyethylene 8320 (Daqing petrochemical company) with the melt mass flow rate of 20g/10min, 5 parts of small particles of methylvinyl silicone rubber 110-1 (Zhejiang Hengchang organosilicon Co., Ltd.) which are crushed after plastication by an open mill, 1 part of maleic anhydride (Shandong Zizipozidan chemical Co., Ltd.), and 0.05 part of organic peroxide initiator 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane (Aksu knobel peroxide Co., Ltd.) are uniformly mixed by a high-speed mixer and grafted by a double-screw reaction, wherein the temperature of the grafting reaction is 210 ℃, and the screw rotation speed is 380 rpm.
Preparing a red phosphorus master batch: uniformly mixing 45 parts of 1250-mesh coated red phosphorus, 7 parts of multi-walled carbon nanotubes, 40 parts of PE 100-grade pipeline material, 7 parts of bifunctional modified polyethylene dispersant and 2251 parts of antioxidant B, and granulating the blend at 200 ℃ by using a double-screw extruder to obtain the polyethylene red phosphorus flame-retardant master batch.
The application of the polyethylene red phosphorus master batch in the mine pipe comprises the following steps:
uniformly mixing 10 parts of conductive carbon black HC-80 (Tianjin Rihua chemical Co., Ltd.), 9 parts of the red phosphorus flame-retardant master batch with the formula and 81 parts of PE 100-grade pipeline material PN049 (Zhongsha petrochemical Co., Ltd.), and granulating by using an extruder at 180 ℃ to obtain the flame-retardant antistatic special material. Then, a 110 x 10mm pipe is extruded on a pipeline processing device, the surface resistance, the flame retardant property and the appearance of the pipe are tested according to MT 558.1, the induced stress is 9MPa, the hydrostatic pressure test is 300h (the standard requirement passes the 100h test) is carried out, and relevant data are shown in Table 1.
Example 3
The polyethylene red phosphorus master batch comprises the following raw materials in parts by weight:
1250 mesh coating red phosphorus (Jining city, Yimin chemical plant) 50 parts; 5 parts of multi-wall carbon nano-tube GT-360 (Shandong Dazhu nanometer material Co., Ltd.); 40 parts of PE80 grade pipeline material 3802 powder (Kataler petrochemical); 4.5 parts of bifunctional modified polyethylene dispersant; 0.5 part of antioxidant B215 (BASF).
The preparation method of the polyethylene red phosphorus master batch comprises the following specific steps:
preparing a bifunctional modified polyethylene dispersant: simultaneously, 92 parts of linear low-density polyethylene 2650 (Tianjin petrochemical company), 5 parts of vinyl-terminated polysiloxane 621V 10000 (Jiangxi Lanxing Xinhuo organosilicon Co., Ltd.), 2.7 parts of maleic anhydride (Shandong Zizipoxiangda chemical Co., Ltd.) and 0.3 part of organic peroxide initiator bis (tert-butylperoxydiisopropylbenzene) (Hunan Xiang science Co., Ltd.) with the melt mass flow rate of 50g/10min are uniformly mixed by a high-speed mixer and grafted by a double-screw reaction, wherein the temperature of the grafting reaction is 180 ℃, and the screw rotating speed is 300 rpm.
Preparing a red phosphorus master batch: uniformly mixing 50 parts of 1250-mesh coated red phosphorus, 5 parts of multi-walled carbon nanotubes, 40 parts of PE 80-grade pipeline material, 4.5 parts of bifunctional modified polyethylene dispersant and 2150.5 parts of antioxidant B, and granulating the blend at 190 ℃ by using a double-screw extruder to obtain the polyethylene red phosphorus flame-retardant master batch.
The application of the polyethylene red phosphorus master batch in the mine pipe comprises the following steps:
and (2) uniformly mixing 10 parts of conductive carbon black, 8 parts of the red phosphorus flame-retardant master batch with the formula and 82 parts of PE 100-grade pipeline material, and granulating at 180 ℃ by using an extruder to obtain the flame-retardant antistatic special material. Then, a 110 x 4.2mm pipe is extruded on a pipeline processing device, the surface resistance, the flame retardant property and the appearance of the pipe are tested according to MT 558.1, the induced stress is 9MPa, the hydrostatic pressure test is 300h (the standard requirement passes the 100h test), and the relevant data are shown in Table 1.
Table 1 example application test data
According to MT 558.1 requirement: the surface resistance requirement of the mining PE pipe is less than 1.0 x 106Omega, the average flame combustion time of the alcohol burner combustion test is not more than 3s, 20 ℃, and the hydrostatic pressure test of 100h passes. As can be seen by comparing example 1 with comparative example 1, replacing the PERT charge with 2650 with high flow, the introduction of high flow polyethylene would result in a failure of the hydrostatic test; as can be seen from the examples 1, the comparative examples 3 and the comparative examples 4, the bifunctional modified polyethylene dispersant is not added into the flame-retardant master batch, so that the hydrostatic pressure test does not reach the standard, mainly because the dispersant is not added, the red phosphorus and the carbon nano tube are not uniformly dispersed in a pipeline, and a stress concentration point is easily formed, so that the pipe is easy to crack after being pressed.
The comparison between the embodiment 1 and the comparative examples 2 and 4 shows that the carbon nano tube has a synergistic flame retardant effect and can reduce the surface resistance value of the mining pipe, and the maleic anhydride and polysiloxane bifunctional modified polyethylene have a dispersing effect, so that the dispersibility of the flame retardant and carbon black in the pipe material is improved, the brightness of the appearance of the pipe material is improved, and the passing rate of a hydrostatic test is improved.
From the examples 1 to 3, it can be seen that the polyethylene red phosphorus master batch disclosed by the invention has the advantages of good flame retardant effect, low surface resistance, strong hydrostatic pressure resistance, bright appearance and the like when being used for mining pipelines under the synergistic effect of the carbon nano tubes and the dispersing effect of maleic anhydride and polysiloxane bifunctional modified polyethylene by taking the pipeline material as the basis.
Comparative example 1 and comparative examples 2 to 4 show that in the polyethylene red phosphorus flame-retardant master batch taking pipeline-grade polyethylene as a matrix, the carbon nanotubes and the bifunctional modified polyethylene also have a synergistic effect, and the synergistic effect is specifically shown in the following steps: meanwhile, the pipe (comparative example 4) made of the polyethylene red phosphorus flame-retardant master batch which does not use the carbon nano tube and the bifunctional modified polyethylene has a great hydrostatic pressure difference at 20 ℃ compared with the pipe (comparative examples 2 and 3) made of the polyethylene red phosphorus flame-retardant master batch which only uses the carbon nano tube or the bifunctional modified polyethylene, and the pipe is broken only within 10.6 hours. The average flame combustion time of the pipe (example 1) prepared by using the polyethylene red phosphorus flame-retardant master batch of the carbon nano tube and the bifunctional modified polyethylene is obviously shortened and the flame retardant property is more excellent than that of the pipe (comparative examples 2 and 3) prepared by using the polyethylene red phosphorus flame-retardant master batch of the carbon nano tube or the bifunctional modified polyethylene singly.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A polyethylene red phosphorus flame retardant masterbatch, characterized by comprising: coating red phosphorus, carbon nano tubes, pipeline-grade polyethylene, bifunctional modified polyethylene and an auxiliary agent.
2. The polyethylene red phosphorus flame-retardant master batch according to claim 1, characterized in that, by weight, 40-50 parts of coated red phosphorus, 5-10 parts of carbon nanotubes, 40-50 parts of pipeline-grade polyethylene, 3-7 parts of bifunctional modified polyethylene and 0.3-2 parts of auxiliary agent;
preferably, by weight, 40-45 parts of coated red phosphorus, 7-10 parts of carbon nano tubes, 40-45 parts of pipeline-grade polyethylene, 4.7-7 parts of bifunctional modified polyethylene and 0.3-1 part of auxiliary agent;
preferably, by weight, 45 parts of coated red phosphorus, 7 parts of carbon nanotubes, 40 parts of pipeline-grade polyethylene, 47 parts of bifunctional modified polyethylene and 1 part of auxiliary agent.
3. The polyethylene red phosphorus flame retardant masterbatch as claimed in claim 1, wherein the coated red phosphorus is melamine resin coated red phosphorus, the content of red phosphorus in the coated red phosphorus is not less than 80%, and the particle size of the coated red phosphorus is 500-2000 mesh;
preferably, the carbon nanotubes are selected from at least one of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes;
preferably, the pipeline-grade polyethylene is high-density polyethylene, and is selected from at least one of PE 80-grade polyethylene, PE 100-grade polyethylene, type I PE-RT and type II PE-RT;
preferably, the bifunctional modified polyethylene is polysiloxane, maleic anhydride modified polyethylene;
preferably, the auxiliary agent is at least one of an antioxidant and a light stabilizer.
4. The polyethylene red phosphorus flame-retardant master batch as claimed in claim 1, wherein the difunctional modified polyethylene dispersant is prepared by grafting 92-97 parts of polyethylene with a melt mass flow rate of 5-50g/10min, 2-5 parts of polysiloxane, 1-3 parts of maleic anhydride and 0.02-0.3 part of organic peroxide initiator through a twin-screw reaction, wherein the temperature of the grafting reaction is 180-250 ℃, and the rotation speed of the screw is 300-500 rpm;
preferably, the polysiloxane is selected from at least one of vinyl-terminated polysiloxane 621V 20000, methyl vinyl silicone rubber 110-1 and vinyl-terminated polysiloxane 621V 10000;
preferably, the organic peroxide initiator is selected from at least one of dicumyl peroxide, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, di-t-butylperoxy diisopropylbenzene.
5. The method for preparing the polyethylene red phosphorus flame retardant master batch as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps: uniformly mixing the coated red phosphorus, the carbon nano tube, the pipeline-grade polyethylene, the bifunctional modified polyethylene and the auxiliary agent, then carrying out melt blending on the blend at the temperature of 170-200 ℃ by using a double-screw extruder, and granulating to obtain the polyethylene red phosphorus flame-retardant master batch;
preferably, the granulation temperature is 200 ℃.
6. A mining pipe comprising carbon black, the polyethylene red phosphorus flame retardant masterbatch of claim, and a pipe grade polyethylene;
preferably, 9-12 parts of carbon black, 8-10 parts of polyethylene red phosphorus flame-retardant master batch and 80-85 parts of pipeline-grade polyethylene by weight.
7. The mining pipe of claim 6, wherein the mining pipe comprises a polyethylene solid-wall pipe, a steel wire mesh skeleton reinforced polyethylene composite pipe, a polyethylene mesh steel belt composite pipe, a steel belt reinforced spiral corrugated pipe, a 3PE anti-corrosion pipe and a high-density polyethylene outer protection pipe.
8. A preparation method of a mining pipe is characterized by comprising the following steps: uniformly mixing carbon black, polyethylene red phosphorus flame-retardant master batch and pipeline-grade polyethylene, granulating at 180-200 ℃ by using an extruder to obtain the flame-retardant antistatic special material, and extruding the pipe material by using pipeline processing equipment.
9. Use of the polyethylene red phosphorus flame retardant masterbatch according to any one of claims 1 to 4 for the preparation of pipes.
10. A secondary pipe network system and/or a hot water system of a hot spring pipeline and/or an air conditioner water inlet and return heat insulation pipeline system and/or an indoor and outdoor water supply pipe network and/or low-temperature ground radiation heating, which is characterized by comprising the polyethylene red phosphorus flame-retardant master batch as defined in any one of claims 1 to 4 and/or the mining pipe as defined in claim 6.
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