CN110144112B - Halogen-free cable material, preparation method thereof and cable containing halogen-free cable material - Google Patents
Halogen-free cable material, preparation method thereof and cable containing halogen-free cable material Download PDFInfo
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- CN110144112B CN110144112B CN201910400252.6A CN201910400252A CN110144112B CN 110144112 B CN110144112 B CN 110144112B CN 201910400252 A CN201910400252 A CN 201910400252A CN 110144112 B CN110144112 B CN 110144112B
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
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- C08L2201/22—Halogen free composition
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Abstract
The invention provides a halogen-free cable material, a preparation method thereof and a cable containing the halogen-free cable material. The halogen-free cable material comprises the following components in percentage by weight of the total weight of the halogen-free cable material: thermoplastic polyurethane: 30-60%, preferably 40-50%; maleic anhydride grafted styrenic elastomer: 5-15%, preferably 7-12%; amino-grafted styrenic elastomer: 3-6%, preferably 3-5%; ethylene acrylate copolymer: 2-10%, preferably 4-8%; flame retardant: 10-35%, preferably 15-30%; hydrolysis resistance agent: 1 to 2%, preferably 1.2 to 1.8%. The halogen-free cable material has the characteristics of low hardness, low crystallization speed and high production efficiency. Furthermore, the halogen-free cable material disclosed by the invention is excellent in tensile strength, tearing performance, thermal shock and thermal aging performance, and can meet various requirements of the halogen-free cable material.
Description
Technical Field
The invention relates to a halogen-free cable material, a preparation method thereof and a cable containing the halogen-free cable material, belonging to the field of high polymer materials.
Background
Thermoplastic Polyurethane (TPU) has become one of the important Thermoplastic elastomer materials due to its excellent properties and wide application. The TPU material has excellent mechanical properties, good biocompatibility and weather resistance, and has no alternative position in some application occasions with severe environment and the medical field. With the continuous improvement of environmental awareness, the production and marketing of TPU as the best PVC substitute product are also rapidly increased, so that the application prospect of TPU is very wide.
TPU has a long history of use in the cable field and is used by many users due to its high strength and safety and environmental protection. In addition to the steady increase of the application amount in the traditional industry, the share of TPU products is also increasing in industries such as new energy automobiles and industrial robots. There are also more and more application fields beginning to pay attention to the TPU halogen-free cable material, such as industries of consumer electronics and optical communication. However, the crystallization of TPU, i.e. the spontaneous crystallization characteristic after stopping movement in a molten state, causes a problem that the machine cannot be started up smoothly after temporary shutdown, and greatly affects the production efficiency.
The physical properties of the TPU product depend largely on the proportion of its hard segment component (MDI) and the crystallization rate of the TPU is largely related to this, so that the lower the content of MDI component, the slower the crystallization rate of the TPU, but at the same time the relatively poorer the physical properties. This conflict limits the production efficiency. Therefore, the market has a strong demand for low hardness high performance slow crystallizing TPU materials.
Disclosure of Invention
Problems to be solved by the invention
The invention aims to overcome the defects in the prior art, and firstly provides a halogen-free cable material which has the characteristics of low hardness and low crystallization speed.
Furthermore, the invention also provides a preparation method of the halogen-free cable material, which has lower requirements on equipment and simpler preparation method and is suitable for mass production.
Means for solving the problems
The invention provides a halogen-free cable material, which comprises the following components in percentage by weight:
thermoplastic polyurethane: 30-60%, preferably 40-50%;
maleic anhydride grafted styrenic elastomer: 5-15%, preferably 7-12%;
amino-grafted styrenic elastomer: 3-6%, preferably 3-5%;
ethylene acrylate copolymer: 2-10%, preferably 4-8%;
flame retardant: 10-35%, preferably 15-30%;
hydrolysis resistance agent: 1 to 2%, preferably 1.2 to 1.8%.
According to the halogen-free cable material, in the halogen-free cable material, the thermoplastic polyurethane is prepared from raw materials including diphenylmethane diisocyanate, polyol and a chain extender; wherein, based on the total weight of the thermoplastic polyurethane, the content of the diphenylmethane diisocyanate is 40-50%, the content of the polyol is 45-55%, and the content of the chain extender is 1-5%.
The halogen-free cable material comprises a styrene elastomer in the maleic anhydride grafted styrene elastomer and/or the amino grafted styrene elastomer, wherein the styrene elastomer in the maleic anhydride grafted styrene elastomer and/or the amino grafted styrene elastomer comprises one or more of hydrogenated poly (styrene-b-isoprene), hydrogenated poly (styrene-b-butadiene-b-styrene), hydrogenated poly (styrene-b-isoprene-b-styrene) and hydrogenated poly (styrene-b-isoprene/butadiene-b-styrene).
The halogen-free cable material is prepared by polymerizing ethylene and at least one of ethyl acrylate, 2-ethyl methacrylate and butyl acrylate.
The halogen-free cable material comprises one or more of melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, phosphate and inorganic phosphate.
The halogen-free cable material according to the present invention, wherein the hydrolysis resistance agent comprises polycarbodiimide.
The halogen-free cable material comprises a halogen-free cable material, wherein the halogen-free cable material further comprises one or a combination of more than two of an antioxidant, a surface treatment agent and a coloring agent, and the addition amount of the antioxidant is 0.3-1.5%, the addition amount of the surface treatment agent is 0.5-1.5% and the addition amount of the coloring agent is 1-2% based on the total weight of the halogen-free cable material; preferably, the first and second electrodes are formed of a metal,
the antioxidant comprises one or the combination of more than two of aromatic amine antioxidant, hindered phenol antioxidant and auxiliary antioxidant;
the surface treating agent comprises one of carrier-free silicone master batch, stearic acid, oleamide, erucamide and the like.
The halogen-free cable material comprises aromatic amine antioxidants, aromatic amine antioxidants and a halogen-free cable material, wherein the aromatic amine antioxidants comprise one or a combination of more than two of diphenylamine, p-phenylenediamine and dihydroquinoline;
the hindered phenol antioxidant comprises one or the combination of more than two of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and N, N' -bis- (3- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionyl) hexanediamine;
the auxiliary antioxidant comprises one or the combination of more than two of trioctyl ester, tridecyl ester, and tridodecyl alcohol ester.
The invention also provides a preparation method of the halogen-free cable material, which comprises the step of mixing the components of the halogen-free cable material.
The invention also provides a cable which comprises the halogen-free cable material.
ADVANTAGEOUS EFFECTS OF INVENTION
The halogen-free cable material has the characteristics of low hardness, low crystallization speed and high production efficiency.
Furthermore, the halogen-free cable material disclosed by the invention is excellent in tensile strength, tearing performance, thermal shock and thermal aging performance, and can meet various requirements of the halogen-free cable material.
Furthermore, the preparation method of the halogen-free cable material has the advantages of easily available raw materials, low equipment requirement and simple and convenient preparation method, and is suitable for mass production.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
The invention firstly provides a halogen-free cable material, which comprises the following components in percentage by weight:
thermoplastic polyurethane: 30-60%, preferably 40-50%;
maleic anhydride grafted styrenic elastomer: 5-15%, preferably 7-12%;
amino-grafted styrenic elastomer: 3-6%, preferably 3-5%;
ethylene acrylate copolymer: 2-10%, preferably 4-8%;
flame retardant: 10-35%, preferably 15-30%;
hydrolysis resistance agent: 1 to 2%, preferably 1.2 to 1.8%.
The halogen-free cable material has the characteristics of low hardness, low crystallization speed and high production efficiency.
According to the invention, the thermoplastic polyurethane is used as the base material, so that the physical properties of the halogen-free cable material can be improved. Specifically, based on the total weight of the halogen-free cable material, the addition amount of the thermoplastic polyurethane is 30-60%, and preferably 40-50%; for example: the thermoplastic polyurethane may be added in an amount of 35%, 40%, 45%, 50%, 55%, 60%, etc. When the addition amount of the thermoplastic polyurethane is less than 30%, the mechanical properties of the final finished product are low; when the amount of the thermoplastic polyurethane added is more than 60%, the crystallization rate is affected by the characteristics of the thermoplastic polyurethane itself.
In the invention, the thermoplastic polyurethane is prepared from raw materials comprising diphenylmethane diisocyanate, polyol and a chain extender; wherein, based on the total weight of the thermoplastic polyurethane, the content of the diphenylmethane diisocyanate is 40-50%, the content of the polyol is 45-55%, and the content of the chain extender is 1-5%.
In the present invention, thermoplastic polyurethane having a relatively high hardness and high physical properties is preferably used. For example: thermoplastic polyurethane sold under the trademark 1185A by Pasteur, thermoplastic polyurethane sold under the trademark 85P4394 by Hensmei, thermoplastic polyurethane sold under the trademark M85 by Gimeray, and the like.
The invention reduces the hardness of the halogen-free cable material by using the styrene elastomer grafted by maleic anhydride, and can effectively avoid the defects of quick crystallization and high hardness caused by using thermoplastic polyurethane. The styrene elastomer grafted with maleic anhydride can be prepared by mixing maleic anhydride and styrene elastomer together.
Specifically, the addition amount of the maleic anhydride grafted styrene elastomer is 5-15%, preferably 7-12% based on the total weight of the halogen-free cable material; for example: the amount of the maleic anhydride-grafted styrene-based elastomer added may be 6%, 8%, 9%, 10%, 11%, 13%, 14%, etc. When the addition amount of the maleic anhydride-grafted styrene-based elastomer is less than 5%, the improvement of the hardness of the material is very limited, and lower hardness cannot be obtained; when the amount is more than 15%, the mechanical properties of the finished product are greatly reduced.
The present invention addresses the compatibility problem between maleic anhydride grafted styrenic elastomers and thermoplastic polyurethanes by using amino grafted styrenic elastomers. The amino functional group of the amino grafted styrene elastomer has stronger affinity with the molecular structure of the thermoplastic polyurethane, and simultaneously, the styrene elastomer can be compatible with the styrene elastomer grafted by maleic anhydride, and can play a role of a compatilizer. Therefore, the use of the amino-grafted styrenic elastomer can effectively solve the problem of the decrease in physical properties due to the incompatibility between the maleic anhydride-grafted styrenic elastomer and the thermoplastic polyurethane.
Specifically, the adding amount of the amino grafted styrene elastomer is 3-6%, preferably 3-5% based on the total weight of the halogen-free cable material; for example, the amino-grafted styrenic elastomer may be added in an amount of 3.5, 4%, 4.5%, 5.5%, etc. When the amount of the amino-grafted styrenic elastomer added is less than 3%, its content as a compatibilizer is insufficient, causing phase separation of the finished product, resulting in a decrease in mechanical properties and overall nonuniformity; when the amount is more than 6%, the compatibility is extremely limited, but the mechanical strength is lowered.
In the present invention, the styrene-based elastomer in the maleic anhydride-grafted styrene-based elastomer and the styrene-based elastomer in the amino group-grafted styrene-based elastomer may be the same or different. Preferably, the styrenic elastomer in the maleic anhydride-grafted styrenic elastomer and/or the amino-grafted styrenic elastomer may include one or a combination of two or more of hydrogenated poly (styrene-b-isoprene), hydrogenated poly (styrene-b-butadiene-b-styrene), hydrogenated poly (styrene-b-isoprene-b-styrene), and hydrogenated poly (styrene-b-isoprene/butadiene-b-styrene).
The crystallization speed of the halogen-free cable material can be changed by adding the ethylene acrylate copolymer. Meanwhile, the styrene elastomer grafted by maleic anhydride reduces the hardness of the material, and can effectively reduce the influence of quick crystallization and high hardness brought by the thermoplastic polyurethane base material.
Specifically, the addition amount of the ethylene acrylate copolymer is 2-10%, preferably 4-8% based on the total weight of the halogen-free cable material. For example, the amount of the ethylene acrylate copolymer added may be 3%, 5%, 6%, 7%, 9%, etc. When the amount of the ethylene acrylate copolymer added is less than 2%, the effect of improving the crystallization rate is limited, and the crystallization rate cannot be significantly slowed; on the other hand, when the amount is more than 10%, the physical properties of the material are deteriorated and defects on the surface of the material are caused.
Preferably, the ethylene acrylate copolymer is obtained by polymerizing ethylene with at least one of ethyl acrylate, 2-ethyl methacrylate and butyl acrylate. The polymerization may be radical polymerization, and specifically, it may be a high molecular weight polymer obtained by radical polymerization by adding oxygen or a peroxide as an initiator.
Flame retardants, preferably halogen-free flame retardants, may also be added in the present invention. Based on the total weight of the halogen-free cable material, the addition amount of the flame retardant is 10-35%, preferably 15-30%; for example, the flame retardant may be added in an amount of 12%, 18%, 20%, 22%, 25%, 28%, 32%, etc. When the addition amount of the flame retardant is less than 10%, the flame retardant performance is low, and the requirement of high flame retardant grade cannot be met; when the amount of the flame retardant is more than 35%, the flame retardant is filled in an excessive amount to cause deterioration of physical properties and surface defects of the material.
In the present invention, the flame retardant includes one or a combination of two or more of melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, phosphate ester, inorganic phosphate, and the like.
The invention also adds an anti-hydrolysis agent. The hydrolysis resistance agent can effectively reduce the influence on the physical properties of the thermoplastic polyurethane during mixing in the extruder. Based on the total weight of the halogen-free cable material, the addition amount of the hydrolysis resistant agent is 1-2%, preferably 1.2-1.8%. For example: the added amount of the hydrolysis resistant agent may be 1.1%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.9%, etc. When the addition amount of the hydrolysis resistant agent is less than 1%, the polyurethane structure cannot be fully protected from hydrolytic damage during mixing due to insufficient addition amount; when the amount is more than 2%, some hydrolysis resistant agents such as polycarbodiimide generate smoke, are inefficient and are not environment-friendly.
Preferably, the hydrolysis resistance agent comprises polycarbodiimide. The polycarbodiimide is a compound formed by dehydrating and polycondensing thiourea under certain conditions by losing hydrogen sulfide or carbamide.
In addition, other auxiliary agents can be added into the halogen-free cable material, and the content of the other auxiliary agents can be 0.1-5% by the total weight of the halogen-free cable material. For example, in the present invention, the halogen-free cable material may further include one or a combination of two or more of an antioxidant, a surface treatment agent, and a colorant. Based on the total weight of the halogen-free cable material, the addition amount of the antioxidant is 0.3-1.5%, the addition amount of the surface treatment agent is 0.5-1.5%, and the addition amount of the colorant is 1-2%.
Preferably, the antioxidant comprises one or a combination of more than two of aromatic amine antioxidant, hindered phenol antioxidant and auxiliary antioxidant; the surface treating agent comprises one of carrier-free silicone master batch, stearic acid, oleamide, erucamide and the like; the colorant comprises toner and/or color masterbatch.
In the invention, the aromatic amine antioxidant comprises one or the combination of more than two of diphenylamine, p-phenylenediamine and dihydroquinoline; the hindered phenol antioxidant comprises one or more of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and N, N' -bis- (3- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionyl) hexanediamine (antioxidant 1098); the auxiliary antioxidant comprises one or the combination of more than two of trioctyl ester, tridecyl ester, and tridodecyl alcohol ester.
The invention screens the selected flame retardant and other additives (antioxidant, surface treating agent, coloring agent, etc.) to ensure compatibility with thermoplastic polyurethane, maleic anhydride grafted styrene elastomer and amino grafted styrene elastomer.
The halogen-free cable material has low hardness (the hardness is less than or equal to 80SHORE A at 25 ℃), slow crystallization speed and good flame retardance and physical properties, namely, the requirement of flame retardance V-0 in UL94 is met. The halogen-free cable material has high mechanical property, the tensile strength is more than or equal to 20MPa, the tearing strength is more than or equal to 30N/mm, and the preferable tearing strength is more than or equal to 40N/mm. In addition, the halogen-free cable material has good processing performance, surface effect and oil resistance, can be repeatedly used, and can be widely applied to the fields of industrial control cables, electronic cables, optical cables and the like.
The invention also provides a preparation method of the halogen-free cable material, which comprises the step of mixing the components of the halogen-free cable material.
Specifically, the preparation method comprises the following steps:
weighing various raw materials according to the weight percentage of the halogen-free cable material;
drying the weighed raw materials in a honeycomb rotary dehumidifier, wherein the thermoplastic polyurethane, the amino grafted styrene elastomer and the maleic anhydride grafted styrene elastomer are dried for 1 to 3 hours at the temperature of between 90 and 110 ℃, and the water content is lower than 200 ppm. Drying the rest raw materials such as the ethylene acrylate copolymer, the flame retardant, the hydrolysis resistant agent and the like at 75-95 ℃ for 2-6 hours.
After drying is finished, sequentially adding thermoplastic polyurethane, amino-grafted styrene elastomer and maleic anhydride-grafted styrene elastomer into a high-speed mixer, then adding the rest raw materials such as ethylene acrylate copolymer, flame retardant, hydrolysis resistant agent and the like, starting high-speed mixing for 1-5 min, observing whether the raw materials are uniformly mixed or not, and discharging after uniform mixing to obtain a mixture;
putting the uniformly mixed mixture into a feeder of a double-screw extruder for extrusion granulation to obtain a halogen-free cable material; wherein the extrusion temperature of the double-screw extruder is 170-200 ℃, and the screw rotating speed is 180-240 r/min.
The invention also provides a cable which comprises the halogen-free cable material.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In the examples 1 to 4, the following examples were carried out,
thermoplastic polyurethane, manufacturer: basff corporation; the trade mark is as follows: 1185A;
amino-grafted styrenic elastomers, manufacturer: asahi Chemicals Inc.; the trade mark is as follows: tuftec MP 10;
maleic anhydride grafted styrenic elastomer, manufacturer: li changrong chemical industry gmbh, trade mark: 9901;
ethylene acrylate copolymer, manufacturer: dupont: reference number 1125.
In comparative example 1, thermoplastic polyurethane, manufacturer: hensmai Corp; the trade mark is as follows: 85P 4394.
In comparative example 2, thermoplastic polyurethane, manufacturer: basff corporation; the trade mark is as follows: 1185A.
Example 1
The halogen-free cable material is prepared by weighing 42 parts of thermoplastic polyurethane, 6 parts of amino-grafted styrene elastomer, 15 parts of maleic anhydride-grafted styrene elastomer, 4 parts of ethylene acrylate copolymer, 15 parts of flame retardant phosphate, 15 parts of melamine cyanurate, 1.5 parts of hydrolysis resistant agent polycarbodiimide, 1 part of carrier-free silicone master batch, 10980.2 parts of antioxidant and 10100.3 parts of antioxidant, wherein the total weight of the halogen-free cable material is 100 parts.
The thermoplastic polyurethane, the amino grafted styrene elastomer and the maleic anhydride grafted styrene elastomer are dried in a honeycomb rotary dehumidifier at 100 ℃ for 2 hours. Drying the ethylene acrylate copolymer, the flame retardant, the hydrolysis resistant agent, the carrier-free silicone master batch, the antioxidant 1098 and the antioxidant 1010 in a vacuum drying bin at the temperature of 75 ℃ for 4 hours.
After drying, firstly adding thermoplastic polyurethane, amino grafted styrene elastomer and maleic anhydride grafted styrene elastomer into a high-speed mixer, then adding ethylene acrylate copolymer, flame retardant, hydrolysis resistant agent, carrier-free silicone master batch, antioxidant 1098 and antioxidant 1010, mixing for 2min, uniformly discharging, and obtaining a mixture.
Pouring the uniformly mixed mixture into a feeder of a double-screw extruder, and granulating to obtain a halogen-free cable material; wherein the main machine rotating speed of the double-screw extruder is 200r/min, and the extrusion temperature is 190 ℃.
Drying the produced halogen-free cable material in a drying bin at 105 ℃ for more than 2h, taking out, approximately and evenly dividing into two parts, wherein one part is used for testing the crystallization hardening speed, the other part is subjected to injection molding, putting the two parts in an oven, tempering the two parts at 80 ℃ for 24 hours, taking out, standing the two parts at room temperature for stabilization, and then measuring indexes such as hardness, tensile strength, flame retardance and the like.
Example 2
Weighing the raw materials, 44 parts of thermoplastic polyurethane, 5 parts of amino grafted styrene elastomer, 12 parts of maleic anhydride grafted styrene elastomer, 6 parts of ethylene acrylate copolymer, 15 parts of flame retardant phosphate and 15 parts of melamine cyanurate, 1.5 parts of hydrolysis resistant agent polycarbodiimide, 1 part of carrier-free silicone master batch, 10980.2 parts of antioxidant and 10100.3 parts of antioxidant, wherein the total weight of the halogen-free cable material is 100 parts.
The thermoplastic polyurethane, the amino grafted styrene elastomer and the maleic anhydride grafted styrene elastomer are dried in a honeycomb rotary dehumidifier at 105 ℃ for 2 hours. Drying the ethylene acrylate copolymer, the flame retardant, the hydrolysis resistant agent, the carrier-free silicone master batch, the antioxidant 1098 and the antioxidant 1010 in a vacuum drying bin at the temperature of 75 ℃ for 4 hours.
After drying, firstly adding thermoplastic polyurethane, amino grafted styrene elastomer and maleic anhydride grafted styrene elastomer into a high-speed mixer, then adding ethylene acrylate copolymer, flame retardant, hydrolysis resistant agent, carrier-free silicone master batch, antioxidant 1098 and antioxidant 1010, mixing for 2min, uniformly discharging, and obtaining a mixture.
Pouring the uniformly mixed mixture into a feeder of a double-screw extruder, and granulating to obtain a halogen-free cable material; wherein the main machine rotating speed of the double-screw extruder is 200r/min, and the extrusion temperature is 190 ℃.
Drying the produced halogen-free cable material in a drying bin at 105 ℃ for more than 2h, taking out, approximately and evenly dividing into two parts, wherein one part is used for testing the crystallization hardening speed, the other part is subjected to injection molding, putting the two parts in an oven, tempering the two parts at 80 ℃ for 24 hours, taking out, standing the two parts at room temperature for stabilization, and then measuring indexes such as hardness, tensile strength, flame retardance and the like.
Example 3
Weighing 47 parts of thermoplastic polyurethane, 4 parts of amino grafted styrene elastomer, 8 parts of maleic anhydride grafted styrene elastomer, 8 parts of ethylene acrylate copolymer, 15 parts of flame retardant phosphate, 15 parts of melamine cyanurate, 1.5 parts of hydrolysis resistant agent polycarbodiimide, 1 part of carrier-free silicone master batch, 10980.2 parts of antioxidant and 10100.3 parts of antioxidant, wherein the total weight of the halogen-free cable material is 100 parts.
The thermoplastic polyurethane, the amino grafted styrene elastomer and the maleic anhydride grafted styrene elastomer are dried in a honeycomb rotary dehumidifier at 105 ℃ for 2 hours. Drying the ethylene acrylate copolymer, the flame retardant, the hydrolysis resistant agent, the carrier-free silicone master batch, the antioxidant 1098 and the antioxidant 1010 in a vacuum drying bin at 75 ℃ for 4 hours.
After drying, firstly adding thermoplastic polyurethane, amino grafted styrene elastomer and maleic anhydride grafted styrene elastomer into a high-speed mixer, then adding ethylene acrylate copolymer, flame retardant, hydrolysis resistant agent, carrier-free silicone master batch, antioxidant 1098 and antioxidant 1010, mixing for 2min, uniformly discharging, and obtaining a mixture.
Pouring the uniformly mixed mixture into a feeder of a double-screw extruder, and granulating to obtain a halogen-free cable material; wherein the rotating speed of a main machine of the double-screw extruder is 200r/min, and the extrusion temperature is 190 ℃;
drying the produced halogen-free cable material in a drying bin at 105 ℃ for more than 2h, taking out, approximately and evenly dividing into two parts, wherein one part is used for testing the crystallization hardening speed, the other part is subjected to injection molding, putting the two parts in an oven, tempering the two parts at 80 ℃ for 24 hours, taking out, standing the two parts at room temperature for stabilization, and then measuring indexes such as hardness, tensile strength, flame retardance and the like.
Example 4
Weighing the raw materials, by taking the total weight of the halogen-free cable material as 100 parts, 48 parts of thermoplastic polyurethane, 3 parts of amino-grafted styrene elastomer, 6 parts of maleic anhydride-grafted styrene elastomer, 10 parts of ethylene acrylate copolymer, 15 parts of flame retardant phosphate, 15 parts of melamine cyanurate, 1.5 parts of hydrolysis resistant agent polycarbodiimide, 1 part of carrier-free silicone master batch, 10980.2 parts of antioxidant and 10100.3 parts of antioxidant.
The thermoplastic polyurethane, the amino grafted styrene elastomer and the maleic anhydride grafted styrene elastomer are dried in a honeycomb rotary dehumidifier at 105 ℃ for 2 hours. Drying the ethylene acrylate copolymer, the flame retardant, the hydrolysis resistant agent, the carrier-free silicone master batch, the antioxidant 1098 and the antioxidant 1010 in a vacuum drying bin at the temperature of 75 ℃ for 4 hours.
After drying, firstly adding thermoplastic polyurethane, amino grafted styrene elastomer and maleic anhydride grafted styrene elastomer into a high-speed mixer, then adding ethylene acrylate copolymer, flame retardant, hydrolysis resistant agent, carrier-free silicone master batch, antioxidant 1098 and antioxidant 1010, mixing for 2min, uniformly discharging, and obtaining a mixture.
Pouring the uniformly mixed raw materials into a feeder of a double-screw extruder, and granulating to obtain a halogen-free cable material; wherein the main machine rotating speed of the double-screw extruder is 200r/min, and the extrusion temperature is 190 ℃.
Drying the produced halogen-free cable material in a drying bin at 105 ℃ for more than 2h, taking out, approximately and evenly dividing into two parts, wherein one part is used for testing the crystallization hardening speed, the other part is subjected to injection molding, putting the two parts in an oven, tempering the two parts at 80 ℃ for 24 hours, taking out, standing the two parts at room temperature for stabilization, and then measuring indexes such as hardness, tensile strength, flame retardance and the like.
Comparative example 1
The halogen-free cable material comprises, by weight, 100 parts of the total weight of the halogen-free cable material, 68.4 parts of thermoplastic polyurethane (manufacturer: Hensmei company; brand: 85P4394), 15 parts of flame retardant phosphate, 15 parts of melamine cyanurate, 0.3 part of antioxidant 1098 and antioxidant 1010, and 1 part of carrier-free silicone master batch.
Drying thermoplastic polyurethane in a vacuum drying bin at 100 ℃ for 2 hours, adding the thermoplastic polyurethane, a flame retardant, an antioxidant and carrier-free silicone master batches into a high-speed mixer, stirring at a high speed for 2min, uniformly mixing, and discharging to obtain a mixture; introducing the uniformly mixed mixture into a feeder of a double-screw extruder, and granulating to obtain a halogen-free cable material; wherein the main machine rotating speed of the double-screw extruder is 200r/min, and the extrusion temperature is 200 ℃.
Drying the produced halogen-free cable material in a drying bin at 105 ℃ for more than 2h, taking out, approximately and evenly dividing into two parts, wherein one part is used for testing the crystallization hardening speed, the other part is subjected to injection molding, putting the two parts in an oven, tempering the two parts at 80 ℃ for 24 hours, taking out, standing the two parts at room temperature for stabilization, and then measuring indexes such as hardness, tensile strength, flame retardance and the like.
Comparative example 2
The halogen-free cable material is prepared by weighing raw materials by taking the total weight of the halogen-free cable material as 100 parts, wherein the raw materials comprise 68.4 parts of thermoplastic polyurethane, 15 parts of flame retardant phosphate, 15 parts of melamine cyanurate, 0.3 part of antioxidant 1098 and 0.3 part of antioxidant 1010 respectively, and 1 part of carrier-free silicone master batch.
Drying thermoplastic polyurethane in a vacuum drying bin at 100 ℃ for 2 hours, adding the thermoplastic polyurethane, a flame retardant, an antioxidant and carrier-free silicone master batches into a high-speed mixer, stirring at a high speed for 2min, uniformly mixing, and discharging to obtain a mixture; introducing the uniformly mixed mixture into a feeder of a double-screw extruder, and granulating to obtain a halogen-free cable material; wherein the main machine rotating speed of the double-screw extruder is 200r/min, and the extrusion temperature is 200 ℃.
Drying the produced halogen-free cable material in a drying bin at 105 ℃ for more than 2h, taking out, approximately and evenly dividing into two parts, wherein one part is used for testing the crystallization hardening speed, the other part is subjected to injection molding, putting the two parts in an oven, tempering the two parts at 80 ℃ for 24 hours, taking out, standing the two parts at room temperature for stabilization, and then measuring indexes such as hardness, tensile strength, flame retardance and the like.
Performance testing
The halogen-free cable materials of examples 1-4 and comparative examples 1-2 of the present invention were subjected to a crystal hardening rate test, and performance tests such as hardness, density, tensile strength, elongation, tear strength, thermal shock property, thermal aging property, and flame retardancy were performed, and the test results are shown in table 1.
TABLE 1
As can be seen from Table 1, the halogen-free cable material of the present invention has a slower crystallization speed than that of the conventional slow crystallization product at a lower hardness (80 SHORE A or less), and also has relatively high physical properties and good flame retardant properties, such as excellent tensile strength, tear properties, thermal shock, thermal aging, and the like. In addition, the preparation method is simple and feasible, and provides a choice with high production efficiency for the use occasions of the halogen-free cable material which needs high-performance low-hardness slow crystallization.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (12)
1. A halogen-free cable material is characterized by comprising the following components in percentage by weight based on the total weight of the halogen-free cable material:
thermoplastic polyurethane: 30-60%;
maleic anhydride grafted styrenic elastomer: 5-15%;
amino-grafted styrenic elastomer: 3-6%;
ethylene acrylate copolymer: 2-10%;
flame retardant: 10-35%;
hydrolysis resistance agent: 1 to 2 percent.
2. The halogen-free cable material according to claim 1, wherein the thermoplastic polyurethane is added in an amount of 40-50% by weight based on the total weight of the halogen-free cable material; the addition amount of the maleic anhydride grafted styrene elastomer is 7-12%; the adding amount of the amino grafted styrene elastomer is 3-5%; the addition amount of the ethylene acrylate copolymer is 4-8%; the addition amount of the flame retardant is 15-30%; the addition amount of the hydrolysis resistant agent is 1.2-1.8%.
3. The halogen-free cable material according to claim 1 or 2, wherein in the halogen-free cable material, the thermoplastic polyurethane is prepared from raw materials comprising diphenylmethane diisocyanate, a polyol and a chain extender; wherein, based on the total weight of the thermoplastic polyurethane, the content of the diphenylmethane diisocyanate is 40-50%, the content of the polyol is 45-55%, and the content of the chain extender is 1-5%.
4. The halogen-free cable material according to claim 1 or 2, wherein the styrene-based elastomer in the maleic anhydride grafted styrene-based elastomer and/or the amino grafted styrene-based elastomer comprises one or a combination of two or more of hydrogenated poly (styrene-b-isoprene), hydrogenated poly (styrene-b-butadiene-b-styrene), and hydrogenated poly (styrene-b-isoprene-b-styrene).
5. The halogen-free cable material according to claim 1 or 2, wherein the ethylene acrylate copolymer is obtained by polymerizing ethylene with at least one of ethyl acrylate, 2-ethyl methacrylate and butyl acrylate.
6. The halogen-free cable material according to claim 1 or 2, wherein the flame retardant comprises one or a combination of two or more of melamine cyanurate, magnesium hydroxide, aluminum hydroxide, phosphate and inorganic phosphate.
7. The halogen-free cable material according to claim 1 or 2, wherein the hydrolysis resistance agent comprises polycarbodiimide.
8. The halogen-free cable material according to claim 1 or 2, wherein the halogen-free cable material further comprises one or a combination of more than two of an antioxidant, a surface treatment agent and a colorant, and the antioxidant is added in an amount of 0.3-1.5%, the surface treatment agent is added in an amount of 0.5-1.5%, and the colorant is added in an amount of 1-2% based on the total weight of the halogen-free cable material.
9. The halogen-free cable material according to claim 8, wherein the antioxidant comprises one or a combination of more than two of aromatic amine antioxidant, hindered phenol antioxidant and auxiliary antioxidant;
the surface treating agent comprises one of carrier-free silicone master batch, stearic acid, oleamide and erucamide.
10. The halogen-free cable material according to claim 9, wherein the aromatic amine antioxidant comprises one or a combination of more than two of diphenylamine, p-phenylenediamine and dihydroquinoline;
the hindered phenol antioxidant comprises one or the combination of more than two of 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) thioether, tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and N, N' -bis- (3- (3, 5-di-tertiary butyl-4-hydroxyphenyl) propionyl) hexanediamine;
the auxiliary antioxidant comprises one or the combination of more than two of trioctyl ester, tridecyl ester, and tridodecyl alcohol ester.
11. A method for preparing a halogen free cable material according to any of claims 1-10, comprising the step of mixing the components of the halogen free cable material.
12. A cable comprising the halogen-free cable material according to any one of claims 1 to 10.
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