CN112226049B - Flame-retardant oil-resistant mildew-proof elastomer heat shrinkage pipe material and preparation method of master batch thereof - Google Patents
Flame-retardant oil-resistant mildew-proof elastomer heat shrinkage pipe material and preparation method of master batch thereof Download PDFInfo
- Publication number
- CN112226049B CN112226049B CN202011121300.7A CN202011121300A CN112226049B CN 112226049 B CN112226049 B CN 112226049B CN 202011121300 A CN202011121300 A CN 202011121300A CN 112226049 B CN112226049 B CN 112226049B
- Authority
- CN
- China
- Prior art keywords
- parts
- flame
- mildew
- retardant
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing and a preparation method thereof, wherein the elastomer heat-shrinkable tubing comprises the following raw materials in parts by weight: 20-40 parts of thermoplastic polyester elastomer, 15-30 parts of ethylene acrylic ester rubber, 20-35 parts of composite flame retardant, 8-15 parts of compatilizer, 3-5 parts of masterbatch, 0.5-2 parts of antioxidant, 0.3-1.5 parts of mildew inhibitor and 0-10 parts of acrylic ester rubber. The flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing prepared by the invention has excellent flame retardance, oil resistance and mildew resistance, excellent mechanical property and high and low temperature resistance, and excellent comprehensive performance. The preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch is simple and efficient, is convenient to operate and control, is favorable for industrial production, and has stable product performance.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing and a preparation method thereof.
Background
Along with the development of economy and the progress of science and technology, the heat-shrinkable tube is increasingly widely applied in the fields of automobiles, electronics, electrics, national defense and military industry and the like. However, the existing heat-shrinkable tubing still has the problems of low oil resistance, poor flame retardance and mildew resistance, and poor performances in the aspects of temperature resistance, machinery and the like, so that the use of the heat-shrinkable tubing is limited, and the heat-shrinkable tubing needs to be further improved.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, one of the purposes of the invention is to provide a flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing and a preparation method thereof, wherein the elastomer heat-shrinkable tubing has excellent flame retardance, oil resistance and mildew resistance, excellent mechanical property, high and low temperature resistance and excellent comprehensive performance.
The invention further aims to provide a preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing, which is simple to operate, convenient to control, high in production efficiency and beneficial to industrial production.
One of the purposes of the invention is realized by the following technical scheme:
a flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing comprises the following raw materials in parts by weight:
the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing material disclosed by the invention adopts the thermoplastic polyester elastomer and ethylene acrylate rubber as main raw materials, is matched with a composite flame retardant, a masterbatch, an antioxidant, a mildew preventive and the like, has good compatibility, and is mutually tonifying, so that the prepared flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing material has excellent flame retardance, oil resistance and mildew resistance, excellent mechanical property, high and low temperature resistance and excellent comprehensive performance. The preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch is simple and efficient, is convenient to operate and control, is favorable for industrial production, and has stable product performance.
Further, the compatilizer is at least one of a maleic anhydride grafted ethylene-octene copolymer, an ethylene-acrylic ester-glycidyl acrylate terpolymer and a maleic anhydride-ethylene-acrylic ester terpolymer. By adopting the compatilizer, the invention can obviously improve the binding force among the thermoplastic polyester elastomer, the ethylene acrylic rubber and the composite flame retardant, obviously improve the tensile strength, the elongation at break, the oil resistance and the like of the thermal shrinkage tube material of the elastomer and improve the comprehensive performance of the product.
Further, the hardness of the thermoplastic polyester elastomer is 30-50A, the melting point is 140-160 ℃, and the melt index (190 ℃ C., 2.16 KG) is 3-8 g/10min. The Mooney viscosity (ML1+4, 100 ℃) of the ethylene acrylic rubber is 15-30. The acrylate rubber is preferably, but not limited to, arisaema Roxburghii AR140.
Further, the antioxidant is at least one of antioxidant DSTP, antioxidant DNP, antioxidant 1010, antioxidant 1024 and antioxidant BHT. Preferably, the antioxidant is composed of antioxidant 1010, antioxidant DSTP and antioxidant BHT in the weight ratio of 1-2 to 0.4-0.8 to 1. By adopting the antioxidant, the invention can effectively inhibit the thermal degradation and oxidative degradation of the composite material, improve the surface finish and keep the antioxidant effect for a long time.
Further, the preparation method of the color master batch comprises the following steps: taking 60-70 parts of carrier resin, 5-9 parts of pigment powder, 4-7 parts of dispersing agent and 8-15 parts of synergistic auxiliary agent by weight, and uniformly mixing to form a mixture; then adopting a double-screw extruder, blending, extruding, granulating and drying at 150-190 ℃ to obtain the color master batch.
Further, the carrier resin is composed of LLDPE resin and EBA resin in a weight ratio of 2-3:1.
Further, the dispersing agent is at least one of polyethylene wax and stearate.
Further, the synergistic agent consists of ethylene bis-stearamide, nano titanium dioxide and PVDF resin according to the weight ratio of 1:0.4-0.7:1-1.5. By adopting the synergistic auxiliary agent, the weather resistance, chemical corrosion resistance and high temperature resistance of the color master batch are improved, and the mechanical property of the color master batch is improved. The PVDF resin is preferably, but not limited to, acima Kynar PVDF HSV900.
The masterbatch of the invention adopts LLDPE resin and EVA resin as carrier resin, ethylene bis-stearamide, nano titanium dioxide and PVDF resin as synergistic auxiliary agent, and is matched with other raw materials, when being applied to flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing, the masterbatch has excellent toughening property and weather resistance, and can improve the wear resistance, dimensional stability, oil resistance and mechanical strength of the elastomer heat-shrinkable tubing, so that the impact property of the elastomer heat-shrinkable tubing is improved.
Further, the mildew preventive is at least one of silver ion antibacterial agent, zinc-silver ion composite antibacterial agent and isothiazolinone antibacterial agent. Further, the mildew preventive consists of 2-thiazole-4-yl benzimidazole and silver ion antibacterial agent according to the weight ratio of 1:1.2-2. The mildew preventive disclosed by the invention can be used for greatly improving the mildew resistance of the elastomer heat-shrinkable tubing and prolonging the service life of the elastomer heat-shrinkable tubing.
Further, the composite flame retardant comprises the following raw materials in parts by weight: 20-30 parts of decabromodiphenyl ethane, 7-12 parts of antimonous oxide and 5-10 parts of magnesium hydroxide. Further, the decabromodiphenylethane is one of Ke poly FM2100R or ya Bao 8010. The antimonous oxide is astrol or flash star antimonous oxide with the purity of more than 99.8 percent; the magnesium hydroxide is ya bao MAGNIFIN H.
The composite flame retardant can improve the flame retardant property, mechanical property and surface property of the composite material, has good dispersibility and uniform distribution in a flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing system, and improves the comprehensive property and product stability of the elastomer heat-shrinkable tubing.
The other purpose of the invention is realized by the following technical scheme: the preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing master batch comprises the following steps:
(1) Adding the raw materials into a high-speed mixer according to a proportion, and uniformly mixing to obtain a mixture;
(2) And adding the obtained mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch.
Further, in the step (1), the mixing temperature is 60-80 ℃, the rotating speed of the high-speed mixer is 500-800r/min, and the mixing time is 15-30min.
Further, in the step (2), the six-zone temperatures of the twin-screw extruder are respectively: the first interval is 110-130 ℃, the second interval is 120-140 ℃, the third interval is 130-150 ℃, the fourth interval is 140-160 ℃, the fifth interval is 150-170 ℃, and the sixth interval is 150-170 ℃.
The preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch has simple and efficient preparation process, is convenient to operate and control, and is beneficial to industrial production. The invention can ensure that the elastomer heat shrinkage pipe material is extruded stably, has good formability, smooth surface, high glossiness, good appearance and stable product performance by strictly controlling the temperature of each area in the extrusion process.
The invention has the beneficial effects that: the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing material adopts the thermoplastic polyester elastomer and the ethylene acrylic rubber as main raw materials, is matched with a composite flame retardant, a masterbatch, an antioxidant, a mildew preventive and the like, has good compatibility of the raw materials, and is mutually tonifying, so that the prepared flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing material has excellent flame retardance, oil resistance and mildew resistance, excellent mechanical property, high and low temperature resistance and excellent comprehensive performance. The preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch is simple and efficient, is convenient to operate and control, is favorable for industrial production, and has stable product performance.
Detailed Description
The invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, in order to facilitate the understanding of those skilled in the art.
Example 1
A flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing comprises the following raw materials in parts by weight: 30 parts of thermoplastic polyester elastomer, 22 parts of ethylene acrylic rubber, 28 parts of composite flame retardant, 12 parts of compatilizer, 4 parts of masterbatch, 1 part of antioxidant, 0.8 part of mildew inhibitor and 5 parts of acrylic rubber.
Further, the compatilizer consists of a maleic anhydride grafted ethylene-octene copolymer and a maleic anhydride-ethylene-acrylate terpolymer according to the weight ratio of 1:2. The thermoplastic polyester elastomer had a hardness of 44A, a melting point of 150℃and a melt index (190 ℃,2.16 KG) of 4g/10min. The ethylene acrylate rubber has a Mooney viscosity (ML1+4, 100 ℃) of 26. The acrylate rubber is preferably, but not limited to, arisaema Roxburghii AR140.
Further, the antioxidant is composed of antioxidant 1010, antioxidant DSTP and antioxidant BHT according to the weight ratio of 1.5:0.46:1.
Further, the preparation method of the color master batch comprises the following steps: taking 65 parts of carrier resin, 7 parts of pigment powder, 5 parts of dispersing agent and 11 parts of synergistic auxiliary agent according to parts by weight, and uniformly mixing to form a mixture; then adopting a double-screw extruder, blending, extruding, granulating and drying at 170 ℃ to prepare the color master batch.
Further, the carrier resin is composed of LLDPE resin and EBA resin in a weight ratio of 2.5:1. The dispersing agent is composed of polyethylene wax and potassium stearate according to the weight ratio of 1:2. The synergistic agent consists of ethylene bis-stearamide, nano titanium dioxide and PVDF resin according to the weight ratio of 1:0.6:1.2. The PVDF resin is preferably, but not limited to, acima Kynar PVDF HSV900. Further, the LLDPE resin is preferably but not limited to Exxon Mobil LL 6201XR. The EBA resin is preferably, but not limited to, tao Shidu bang 34035.
Further, the mildew preventive consists of 2-thiazole-4-yl benzimidazole and silver ion antibacterial agent according to the weight ratio of 1:1.5.
Further, the composite flame retardant comprises the following raw materials in parts by weight: 25 parts of decabromodiphenyl ethane, 9 parts of antimonous oxide and 7 parts of magnesium hydroxide. Further, the decabromodiphenylethane is Ke poly FM2100R. The antimonous oxide is astronomical antimonous oxide with the purity of more than 99.8 percent. The magnesium hydroxide is ya bao MAGNIFIN H.
The preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing master batch comprises the following steps:
(1) Adding the raw materials into a high-speed mixer according to a proportion, and uniformly mixing to obtain a mixture;
(2) And adding the obtained mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch.
Further, in the step (1), the mixing temperature is 75 ℃, the rotating speed of the high-speed mixer is 600-r/min, and the mixing time is 20min.
Further, in the step (2), the six-zone temperatures of the twin-screw extruder are respectively: one interval 120 ℃, two intervals 130 ℃, three intervals 140 ℃, four intervals 150 ℃, five intervals 160 ℃, six intervals 160 ℃.
Example 2
A flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing comprises the following raw materials in parts by weight: 20 parts of thermoplastic polyester elastomer, 15 parts of ethylene acrylic ester rubber, 20 parts of composite flame retardant, 8 parts of compatilizer, 3 parts of masterbatch, 0.5 part of antioxidant and 0.3 part of mildew inhibitor.
Further, the compatilizer consists of a maleic anhydride grafted ethylene-octene copolymer and a maleic anhydride-ethylene-acrylate terpolymer according to the weight ratio of 1:1. The antioxidant is composed of antioxidant 1010, antioxidant DSTP and antioxidant BHT according to the weight ratio of 1:0.4:1. The thermoplastic polyester elastomer had a hardness of 36A, a melting point of 143℃and a melt index (190℃2.16 KG) of 6g/10min. The ethylene acrylate rubber has a Mooney viscosity (ML1+4, 100 ℃) of 22.
Further, the preparation method of the color master batch comprises the following steps: according to the weight parts, 60 parts of carrier resin, 5 parts of pigment powder, 47 parts of dispersing agent and 8 parts of synergistic auxiliary agent are taken and uniformly mixed to form a mixture; then adopting a double-screw extruder, blending, extruding, granulating and drying at 150 ℃ to prepare the color master batch. Further, the carrier resin is composed of LLDPE resin and EBA resin in a weight ratio of 2:1. The dispersing agent is polyethylene wax.
Further, the synergistic agent consists of ethylene bis-stearamide, nano titanium dioxide and PVDF resin according to the weight ratio of 1:0.4:1.
Further, the mildew preventive consists of 2-thiazole-4-yl benzimidazole and silver ion antibacterial agent according to the weight ratio of 1:1.2.
Further, the composite flame retardant comprises the following raw materials in parts by weight: 20 parts of decabromodiphenyl ethane, 7 parts of antimonous oxide and 5 parts of magnesium hydroxide. Further, the decabromodiphenylethane is poly yabao 8010. The antimonous oxide is flash antimonous oxide with the purity of more than 99.8 percent; the magnesium hydroxide is ya bao MAGNIFIN H.
The preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing master batch comprises the following steps:
(1) Adding the raw materials into a high-speed mixer according to a proportion, and uniformly mixing to obtain a mixture;
(2) And adding the obtained mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch.
Further, in the step (1), the mixing temperature is 60 ℃, the rotating speed of the high-speed mixer is 500-r/min, and the mixing time is 30min.
Further, in the step (2), the six-zone temperatures of the twin-screw extruder are respectively: one section 110 ℃, two sections 120 ℃, three sections 130 ℃, four sections 140 ℃, five sections 150 ℃, six sections 150 ℃.
The rest of this embodiment is the same as embodiment 1, and will not be described here again.
Example 3
A flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing comprises the following raw materials in parts by weight: 40 parts of thermoplastic polyester elastomer, 30 parts of ethylene acrylic ester rubber, 35 parts of composite flame retardant, 15 parts of compatilizer, 5 parts of masterbatch, 2 parts of antioxidant, 1.5 parts of mildew inhibitor and 10 parts of acrylic ester rubber. The thermoplastic polyester elastomer had a hardness of 42A, a melting point of 148℃and a melt index (190℃2.16 KG) of 4g/10min. The ethylene acrylate rubber has a Mooney viscosity (ML1+4, 100 ℃) of 25.
Further, the compatilizer consists of a maleic anhydride grafted ethylene-octene copolymer, an ethylene-acrylic ester-glycidyl acrylate terpolymer and a maleic anhydride-ethylene-acrylic ester terpolymer according to the weight ratio of 1:0.2:1.8.
Further, the preparation method of the color master batch comprises the following steps: taking 70 parts of carrier resin, 9 parts of pigment powder, 7 parts of dispersing agent and 15 parts of synergistic auxiliary agent by weight, and uniformly mixing to form a mixture; then adopting a double-screw extruder, blending, extruding, granulating and drying at 190 ℃ to prepare the color master batch.
Further, the carrier resin is composed of LLDPE resin and EBA resin in a weight ratio of 3:1. The dispersing agent is composed of polyethylene wax and potassium stearate according to the weight ratio of 1:2.
Further, the synergistic agent consists of ethylene bis-stearamide, nano titanium dioxide and PVDF resin according to the weight ratio of 1:0.7:1.5. Furthermore, the mildew preventive consists of 2-thiazole-4-yl benzimidazole and silver ion antibacterial agent according to the weight ratio of 1:2.
Further, the composite flame retardant comprises the following raw materials in parts by weight: 30 parts of decabromodiphenyl ethane, 12 parts of antimonous oxide and 10 parts of magnesium hydroxide. Further, the decabromodiphenylethane is Ke poly FM2100R. The antimonous oxide is astronomical antimonous oxide with the purity of more than 99.8 percent; the magnesium hydroxide is ya bao MAGNIFIN H.
The preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing master batch comprises the following steps:
(1) Adding the raw materials into a high-speed mixer according to a proportion, and uniformly mixing to obtain a mixture;
(2) And adding the obtained mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch.
Further, in the step (1), the mixing temperature is 80 ℃, the rotating speed of the high-speed mixer is 800r/min, and the mixing time is 15min.
Further, in the step (2), the six-zone temperatures of the twin-screw extruder are respectively: one interval 130 ℃, two intervals 140 ℃, three intervals 150 ℃, four intervals 160 ℃, five intervals 170 ℃ and six intervals 170 ℃.
The rest of this embodiment is the same as embodiment 1, and will not be described here again.
Example 4
A flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing comprises the following raw materials in parts by weight: 30 parts of thermoplastic polyester elastomer, 25 parts of ethylene acrylic rubber, 25 parts of composite flame retardant, 12 parts of compatible, 4 parts of masterbatch, 1.5 parts of antioxidant, 1.2 parts of mildew inhibitor and 6 parts of acrylic rubber.
Further, the preparation method of the color master batch comprises the following steps: according to the weight parts, 66 parts of carrier resin, 8 parts of pigment powder, 6 parts of dispersing agent and 12 parts of synergistic auxiliary agent are taken and uniformly mixed to form a mixture; then adopting a double-screw extruder, blending, extruding, granulating and drying at 180 ℃ to prepare the color master batch. Further, the carrier resin is composed of LLDPE resin and EBA resin in a weight ratio of 2.5:1.
Further, the synergistic agent consists of ethylene bis-stearamide, nano titanium dioxide and PVDF resin according to the weight ratio of 1:0.6:1.4.
The rest of this embodiment is the same as embodiment 1, and will not be described here again.
Comparative example 1
The difference between this comparative example and example 1 is that: the color master batch in the comparative example 1 adopts a Kabo characteristic master batch PE2772 to replace the color master batch in the example 1, and the flame retardant in the comparative example adopts a flame retardant SF-100 to replace the composite flame retardant in the example 1. The remainder of this comparative example is the same as in example 1 and will not be described here again.
Comparative example 2
The difference between this comparative example and example 1 is that: this comparative example 1 uses medium petrifaction Yanshan LDPE100-AC instead of the ethylene acrylate rubber in example 1. The remainder of this comparative example is the same as in example 1 and will not be described here again.
The flame-retardant oil-resistant mildew-proof elastomer heat shrinkage pipe materials of examples 1-4 and comparative examples 1-2 are pressed into sheets, and after 12Mrad dose of high-energy electron beam irradiation crosslinking, the test results are as follows:
the liquid resistance measurements in the above table are: the heat-shrinkable tubes prepared by adopting the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube materials of the examples 1-4 and the comparative examples 1-2 are respectively soaked in five liquids, wherein the five liquids are respectively: IRM903 gasoline; hydraulic oil No. 15 (GJB 1177-1991 petroleum-based aviation hydraulic oil); lubricating oil No. 8 (GB 439-1990 aerojet lubricating oil); 5% NaCl solution; the aircraft anti-freezing liquid (GB/T20856-2007 aircraft Newton deicing and anti-icing liquid ISO I type. Examples 1-4 have breakdown strength still greater than 12kv/mm after being subjected to liquid resistance (23 ℃ for 24 hrs) test, the test method is ASTMD 2671, the test tensile strength is more than 12MPa, the elongation at break is more than 250%, the test method is ASTM D638, the comparative example 1-2 has tensile strength more than 11MPa, elongation at break less than 230% after being subjected to liquid resistance (23 ℃ for 24 hrs) test, the tensile strength of comparative example 1 is less than 10.4MPa, and the elongation at break is less than 210%.
The flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing prepared by the invention has excellent flame retardance, oil resistance and mildew resistance, excellent mechanical property and high and low temperature resistance, and excellent comprehensive performance. The preparation method of the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch is simple and efficient, is convenient to operate and control, is favorable for industrial production, and has stable product performance.
The above embodiments are preferred embodiments of the present invention, and besides, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Claims (5)
1. A flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tubing is characterized in that: the material comprises the following raw materials in parts by weight:
20-40 parts of thermoplastic polyester elastomer
15-30 parts of ethylene acrylic rubber
20-35 parts of composite flame retardant
8-15 parts of compatilizer
3-5 parts of color master batch
0.5-2 parts of antioxidant
0.3 to 1.5 portions of mildew preventive
0-10 parts of acrylate rubber;
the composite flame retardant comprises the following raw materials in parts by weight: 20-30 parts of decabromodiphenyl ethane, 7-12 parts of antimonous oxide and 5-10 parts of magnesium hydroxide;
the compatilizer is at least one of maleic anhydride grafted ethylene-octene copolymer, ethylene-acrylic ester-glycidyl acrylate terpolymer and maleic anhydride-ethylene-acrylic ester terpolymer;
the mildew preventive is at least one of a silver ion antibacterial agent, a zinc-silver ion composite antibacterial agent and an isothiazolinone antibacterial agent;
the preparation method of the color master batch comprises the following steps: taking 60-70 parts of carrier resin, 5-9 parts of pigment powder, 4-7 parts of dispersing agent and 8-15 parts of synergistic auxiliary agent by weight, and uniformly mixing to form a mixture; then adopting a double-screw extruder, blending, extruding, granulating and drying at 150-190 ℃ to prepare color master batch; the synergistic agent consists of ethylene bis-stearamide, nano titanium dioxide and PVDF resin according to the weight ratio of 1:0.4-0.7:1-1.5; the carrier resin consists of LLDPE resin and EBA resin according to the weight ratio of 2-3:1; the dispersing agent is at least one of polyethylene wax and stearate.
2. The flame-retardant, oil-resistant and mildew-proof elastomer heat-shrinkable tubing of claim 1, wherein: the antioxidant is at least one of antioxidant DSTP, antioxidant DNP, antioxidant 1010, antioxidant 1024 and antioxidant BHT.
3. A method for preparing the flame-retardant, oil-resistant and mildew-proof elastomer heat-shrinkable tubing material as claimed in any one of claims 1 to 2, which is characterized in that: the method comprises the following steps:
(1) Adding the raw materials into a high-speed mixer according to a proportion, and uniformly mixing to obtain a mixture;
(2) And adding the obtained mixture into a double-screw extruder, and carrying out melt extrusion granulation to obtain the flame-retardant oil-resistant mildew-proof elastomer heat-shrinkable tube master batch.
4. The method for preparing the flame-retardant, oil-resistant and mildew-proof elastomer heat-shrinkable tubing material according to claim 3, which is characterized by comprising the following steps:
the mixing temperature in the step (1) is 60-80 ℃, the rotating speed of the high-speed mixer is 500-800r/min, and the mixing time is 15-30min.
5. The method for preparing the flame-retardant, oil-resistant and mildew-proof elastomer heat-shrinkable tubing material according to claim 3, which is characterized by comprising the following steps: in the step (2), the six-zone temperatures of the twin-screw extruder are respectively: the first interval is 110-130 ℃, the second interval is 120-140 ℃, the third interval is 130-150 ℃, the fourth interval is 140-160 ℃, the fifth interval is 150-170 ℃, and the sixth interval is 150-170 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011121300.7A CN112226049B (en) | 2020-10-19 | 2020-10-19 | Flame-retardant oil-resistant mildew-proof elastomer heat shrinkage pipe material and preparation method of master batch thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011121300.7A CN112226049B (en) | 2020-10-19 | 2020-10-19 | Flame-retardant oil-resistant mildew-proof elastomer heat shrinkage pipe material and preparation method of master batch thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112226049A CN112226049A (en) | 2021-01-15 |
| CN112226049B true CN112226049B (en) | 2023-07-21 |
Family
ID=74117502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011121300.7A Active CN112226049B (en) | 2020-10-19 | 2020-10-19 | Flame-retardant oil-resistant mildew-proof elastomer heat shrinkage pipe material and preparation method of master batch thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112226049B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114350118B (en) * | 2022-01-17 | 2023-06-09 | 成都金发科技新材料有限公司 | TPEE/EMA composition and application thereof |
| CN114656742B (en) * | 2022-04-18 | 2024-05-03 | 西北工业大学 | Preparation method of alloy type creep-resistant fluorine-containing thermoplastic elastomer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696293A (en) * | 2009-10-28 | 2010-04-21 | 江苏达胜热缩材料有限公司 | Semi-conducting low-medium voltage fire retardant single-wall heat-shrinkable tube and preparation method thereof |
| CN102532812A (en) * | 2010-12-16 | 2012-07-04 | 深圳市宏商材料科技股份有限公司 | Diesel oil resistant heat shrinkage sleeve |
| CN103059359A (en) * | 2012-11-20 | 2013-04-24 | 深圳市沃尔核材股份有限公司 | Soft and flexible heat-shrinkable tube with properties of high fire retardance and oil resistance and production method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2621516A1 (en) * | 2005-09-09 | 2007-03-15 | Sumitomo Electric Industries, Ltd. | Flame-retardant resin composition, and electric wire and insulating tube using same |
| US9175159B2 (en) * | 2012-01-19 | 2015-11-03 | Aronkasei Co., Ltd. | Thermoplastic elastomer composition |
| WO2019152830A1 (en) * | 2018-02-01 | 2019-08-08 | Dow Silicones Corporation | Composition, polymer composite article formed therewith, and method of preparing same |
-
2020
- 2020-10-19 CN CN202011121300.7A patent/CN112226049B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101696293A (en) * | 2009-10-28 | 2010-04-21 | 江苏达胜热缩材料有限公司 | Semi-conducting low-medium voltage fire retardant single-wall heat-shrinkable tube and preparation method thereof |
| CN102532812A (en) * | 2010-12-16 | 2012-07-04 | 深圳市宏商材料科技股份有限公司 | Diesel oil resistant heat shrinkage sleeve |
| CN103059359A (en) * | 2012-11-20 | 2013-04-24 | 深圳市沃尔核材股份有限公司 | Soft and flexible heat-shrinkable tube with properties of high fire retardance and oil resistance and production method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 孙邵灿编."塑料实用手册（第1版）".《塑料实用手册（第1版）》.浙江科学技术出版社,1999,第78-79页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112226049A (en) | 2021-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112226049B (en) | Flame-retardant oil-resistant mildew-proof elastomer heat shrinkage pipe material and preparation method of master batch thereof | |
| CN110903535A (en) | Low-smoke halogen-free flame-retardant sheath material with good cold resistance for cable and preparation method thereof | |
| CN102888090A (en) | Halogen-free flam-retardant thermoplastic polyurethane (TPU) material | |
| CN103804798A (en) | Halogen-free flame retardant polyethylene sheath material applied to super high voltage cable and preparation method and application thereof | |
| CN105038087A (en) | Halogen-free flame retardant high-tear-resistance wire and cable compound for electric vehicles and wire and cable production method | |
| CN104004271A (en) | Low-temperature-resistant polypropylene special material | |
| CN109651749A (en) | Resistance to cracking anti-flaming polypropylene material of low-temperature impact-resistant and its preparation method and application | |
| CN105462157A (en) | High-fluidity, scratch-resistant and low-temperature-resistant brominated flame-retardant ABS (acrylonitrile-butadiene-styrene)/TPU (thermoplastic polyurethane) alloy material as well as preparation method and application thereof | |
| CN102532742A (en) | Material special for flame-retardant polyvinyl chloride jacketed cable | |
| CN105001503A (en) | High-extrusion-rate heat-shrinkable tube and production method thereof | |
| CN102898715B (en) | Extremely temperature sensitive halogen-free and low smoke flame retardant plastic alloy for cables and preparation method thereof | |
| CN105199187A (en) | Low-energy-consumption, high-flame-retardancy, low-smoke and halogen-free cable material | |
| CN112759817A (en) | Low-shrinkage halogen-free flame-retardant polyethylene composition and preparation method and application thereof | |
| CN115093670B (en) | Multifunctional composite auxiliary agent for PC (personal computer) | |
| CN104262851A (en) | Wear-resistant irradiation cross-linked polyvinyl chloride (PVC) insulating material for automotive original line and preparation method thereof | |
| CN1793212A (en) | Low smoke non-halogen fire retarding expansive polyolefins electronic wire material and preparation process thereof | |
| CN111675860A (en) | Low-temperature-resistant oil-resistant torsion-resistant high-flame-retardant sheath material and preparation method thereof | |
| CN105131575A (en) | Jamproof shielding-enhanced sheath material for subway communication cable and preparation method of sheath material | |
| CN102146178A (en) | Flame retardant and antistatic polyethylene for mine gas drainage pipeline and preparation method thereof | |
| CN102295797B (en) | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof | |
| CN102690466A (en) | Anti-aging polypropylene material and preparation method thereof | |
| CN1807499A (en) | Halogen-free combustion-proof polypropylene high-speed abrasion-proof insulating material for auto initial line | |
| CN107082971A (en) | A kind of flame retardant type PVC waterproof rolls | |
| CN114031842B (en) | Impact-resistant halogen-free flame-retardant polypropylene composition and preparation method and application thereof | |
| CN102372902A (en) | Epoxy resin enhanced high-temperature resistant polyethylene cable material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |