CN114736451A - Preparation method of high-performance multifunctional cable shielding material - Google Patents
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- CN114736451A CN114736451A CN202210342553.XA CN202210342553A CN114736451A CN 114736451 A CN114736451 A CN 114736451A CN 202210342553 A CN202210342553 A CN 202210342553A CN 114736451 A CN114736451 A CN 114736451A
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- C08L23/0853—Vinylacetate
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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Abstract
The invention relates to a preparation method of a high-performance multifunctional cable shielding material, which comprises the following steps of (1) preparing functional fillers and processing aids in proportion, wherein the functional fillers comprise conductive fillers and other functional fillers; mixing the conductive filler, other functional fillers and processing aids at a high speed, and heating the mixture by using far infrared rays in the high-speed mixing process; step (3) extruding and granulating the mixture processed in the step two to obtain functional particles; and (5) mechanically stirring and uniformly mixing the functional particles and the resin granules in the step (4), and melting and mixing to obtain the high-performance multifunctional cable shielding material. The far infrared heating and high mixing change the action link of the auxiliary agent, so that the auxiliary agent is firstly dispersed and combined with the functional filler, the actual action of the auxiliary agent is more fully exerted along with the dispersion of the filler in the melting processing process of the resin, and the dispersion of the filler in the matrix and the interface combination effect of the filler and the matrix are obviously improved.
Description
Technical Field
The invention belongs to the field of shielding high polymer materials and preparation thereof.
Background
In the field of semiconductive shielding materials for cables, in order to ensure the stability of the resistivity of the materials, the shielding materials are prepared based on a contact conduction mechanism of carbon black particles in a polymer matrix, so that conductive carbon black with a small specific surface area and a medium structure is generally selected, and the addition amount of the conductive carbon black is relatively high and is generally more than 30 wt%. With the development of society, the shielding material for cables with single function is difficult to meet the application requirements of more special fields or places, and in order to further improve the application of the shielding material in the field of protective materials, the multi-functionalization of the shielding material will become the key research direction in the future and is the trend of the future development in the field.
The multifunctional cable shielding material system is characterized in that under the condition of relatively high conductive filler content, other functional fillers are continuously added to form a high-performance composite system, so that the multifunctional cable shielding material system meets the basic performance requirement of the system while ensuring the multiple functions of the multifunctional cable shielding material system. In the composite system, a large amount of micro-nano structure powdery functional filler and auxiliary agent exist, and the micro-nano structure powdery functional filler and auxiliary agent are difficult to be directly and uniformly mixed with resin granules, so that the dispersion and distribution of the resin granules in the processing process are influenced, the preparation of the shielding material for the multifunctional cable with excellent and stable performance is not facilitated, and a lot of uncertainty is brought to production.
Far infrared heating is a quick, simple and energy-saving heating mode, is widely applied to the fields of medical treatment, food, materials and the like, has common functions of drying, sterilization, heating and the like, is a conventional technology in industry, but has not been regarded as important for processing plastics and composite materials thereof by melting and mixing, and particularly as an auxiliary means for improving the characteristics of functional fillers.
Disclosure of Invention
The invention mixes the functional filler and the auxiliary agent, realizes the high-efficiency distribution and combination of the auxiliary agent and the filler by utilizing far infrared rapid heating and high-speed stirring, and can exert the bonding action of the auxiliary agent to realize the granulation of powder after the screw extrusion, thereby obviously improving the dispersion of the filler in resin and the combination effect of the filler and the resin, and preparing the multifunctional cable shielding material with excellent performance (especially basic performance).
The technical scheme adopted by the invention is as follows: a method for preparing a high-performance multifunctional cable shielding material comprises
Preparing functional filler and processing aid in proportion, wherein the functional filler comprises conductive filler and other functional fillers;
step two, mixing the conductive filler, the other functional fillers and the processing aid at a high speed, and heating the mixture by using far infrared rays in the high-speed mixing process;
step three, extruding and granulating the mixture processed in the step two to obtain functional particles;
and step four, mechanically stirring and uniformly mixing the functional particles and the resin granules, and melting and mixing to obtain the high-performance multifunctional cable shielding material.
The conductive filler is selected from at least one of conductive carbon black, conductive graphite, carbon fiber and metal powder; the other functional filler is at least one of flame retardant filler and heat conducting filler.
The flame-retardant filler is selected from at least one of red phosphorus compound flame retardant and intumescent compound flame retardant; the heat conductive filler is selected from at least one of alumina, boron nitride and silicon nitride.
The processing aid is selected from compounds with molecular weight less than 1500 and melting point less than 170 ℃; the processing aid is at least one selected from an antioxidant, a lubricant, a plasticizer, a coupling agent and a dispersing agent.
The antioxidant package is at least one selected from the group consisting of antioxidant 1035, antioxidant 1010, and antioxidant 300: the lubricant is selected from at least one of butyl stearate, zinc stearate, paraffin and ethylene bis stearamide; the plasticizer is selected from at least one of phosphate, phthalate, trimellitate and epoxy glycerol tricarboxylate; the coupling agent is selected from at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
The resin is at least one selected from polypropylene, polyethylene, ethylene-vinyl acetate copolymer and polyolefin thermoplastic elastomer.
The conductive filler content in the material is 20-40 wt%, the other functional fillers content is 10-30 wt%, the processing aid content is 5-15 wt%, and the resin content is 40-60 wt%.
And step two, the power of far infrared radiation heating is 300-800W, the stirring speed of high-speed mixing is 100-500 rpm, and the high-speed mixing time is 1-10 min.
In the third step, the mixture is extruded and granulated by a single screw to obtain the functional particles; the high-performance multifunctional cable shielding material in the fourth step is processed by at least one of a double screw, a triple screw and a reciprocating machine.
The invention has the advantages that:
(1) the rapid phase change (including gasification, liquefaction, melting and the like) of the auxiliary agent is realized by utilizing a far infrared heating technology, and the mass transfer process of the auxiliary agent in the filler can be obviously improved by combining a high-speed mixing process, so that the efficient distribution and combination of the auxiliary agent and functional particles are realized, and the dispersion of the filler in resin in a melting processing process is facilitated.
(2) The functional micro-nano powder can be made into granules (the particle size is 1-5 mm) in the compression process by utilizing the bonding effect of the auxiliary agent which is heated to be in a liquid state or a molten state, so that the filler and the resin granules can be uniformly mixed, more stable feeding is realized, and a product with more stable performance is prepared.
(3) The heated granules have higher temperature, are favorable for forming better interface wetting in the processes of online mixing and melting processing with resin granules, so that the interface between the resin and the filler is more perfect, a better functional filler dispersion network can be realized, and higher mechanical properties are ensured while the functionality is exerted.
(4) Compared with the traditional process of mixing the filler, the resin and the auxiliary agent together, the invention has the advantages that the action link of the auxiliary agent is regulated and optimized in a simple mode, so that the auxiliary agent can play the roles in the aspects of plasticization, lubrication, oxidation resistance, interface combination and the like more fully and more stably.
Drawings
FIG. 1 is a flow chart of the preparation method of the high-performance multifunctional shielding material of the present invention.
Detailed Description
The present invention is described in further detail below with reference to examples, which are intended to be illustrative and not to be construed as limiting the invention.
A preparation method of a high-performance multifunctional cable shielding material comprises the following steps:
(1) weighing the conductive filler, the other functional fillers and the processing aid according to a metering proportion;
(2) secondly, placing the weighed blend in a high-speed mixer with far infrared heating;
(3) then, compressing and extruding the treated blend into functional particles by using a screw extrusion device;
(4) and mechanically stirring and uniformly mixing the functional particles and the resin, and performing melt processing to obtain the material.
The source of the conductive filler and other functional fillers is not particularly limited, and commercially available products known to those skilled in the art may be used.
The auxiliary agent is preferably a compound with the molecular weight of less than 1500 and the melting point of less than 170 ℃; the processing aid preferably comprises at least one of an antioxidant, a lubricant, a plasticizer, a coupling agent and a dispersant, and more preferably a mixture of an antioxidant, a lubricant, a plasticizer and a coupling agent. The invention can correspondingly adjust the dispersibility of the filler and the bonding property of the filler and the interface by adding the processing aid.
The antioxidant comprises at least one of 1035, 1010, and 300; the lubricant preferably includes at least one of butyl stearate, zinc stearate, and ethylene bis stearamide; the plasticizer preferably includes at least one of phosphoric acid ester, phthalic acid ester, trimellitic acid ester, and epoxy glycerol tricarboxylic acid ester; the coupling agent preferably includes at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent.
The content of the conductive filler is preferably 20-40 wt%, and more preferably 25-35 wt%; the content of the other functional fillers is preferably 10-30 wt%, and more preferably 15-25 wt%; the content of the auxiliary agent is preferably 5-15 wt%, and more preferably 8-12 wt%; the resin content is preferably 40 to 60 wt%, and more preferably 45 to 55 wt%.
The power of the far infrared radiation heating device is preferably 300-800W, and more preferably 400-600W; the stirring speed of the high-speed mixer is preferably 100-500 rpm, and more preferably 200-400 rpm; the high mixing time is preferably 1-10 min, and more preferably 3-6 min.
The pelletized mixture is preferably produced using a single screw. The multifunctional shielding material is preferably processed by one of double-screw, triple-screw and reciprocating machines.
Example one
(1) Weighing 32% of conductive carbon black, 16% of intumescent flame retardant and 9% of auxiliary agent (the types and the contents of the auxiliary agent are respectively 7.2% of white oil, 0.5% of zinc stearate, 1% of ethylene bis stearamide and 0.3% of antioxidant 1010);
(2) putting the mixture of the filler and the auxiliary agent into a high-speed mixer with far infrared heating, setting the infrared heating power to be 500W, the stirring speed to be 360rpm, and heating, stirring and mixing for 4 min;
(3) conveying the heated and mixed materials to a hopper, extruding the materials by a single screw rod, and preparing functional granules under the bonding action of an auxiliary agent;
(4) and conveying the functional granules to a double-screw feeding hopper, uniformly stirring the functional granules and 43% of EVA resin in the hopper, conveying the functional granules to a double screw, and performing melt processing at 120 ℃ to obtain the multifunctional shielding material.
Example two
(1) Weighing 32% of conductive carbon black, 16% of intumescent flame retardant and 9% of auxiliary agent (the types and the contents of the auxiliary agent are respectively 7.2% of white oil, 0.5% of zinc stearate, 1% of ethylene bis stearamide and 0.3% of antioxidant 1010);
(2) putting the mixture of the filler and the auxiliary agent into a high-speed mixer with far infrared heating, setting the infrared heating power to be 400W, the stirring speed to be 250rpm, and heating, stirring and mixing for 6 min;
(3) conveying the heated and mixed materials to a hopper, extruding the materials by a single screw rod, and preparing functional granules under the bonding action of an auxiliary agent;
(4) and conveying the mixture granules to a double-screw feeding hopper through a single screw, uniformly stirring the mixture granules with 43% of PE/EVA resin in the hopper, conveying the mixture granules to a double screw, and carrying out melt processing at 120 ℃ to obtain the multifunctional shielding material.
EXAMPLE III
(1) Weighing 30% of conductive carbon black, 15% of heat-conducting filler and 10% of auxiliary agent (the types and the contents of the auxiliary agent are respectively 7.2% of white oil, 0.5% of zinc stearate, 1% of ethylene bis stearamide, 1% of silane coupling agent and 0.3% of antioxidant 1010);
(2) putting the mixture of the filler and the auxiliary agent into a high-speed mixer with far infrared heating, setting the infrared heating power to be 400W, the stirring speed to be 360rpm, and heating, stirring and mixing for 5 min;
(3) conveying the heated and mixed materials to a hopper, extruding the materials by a single screw rod, and preparing functional granules under the bonding action of an auxiliary agent;
(4) and conveying the mixture granules to a double-screw feeding hopper through a single screw, uniformly stirring and mixing the mixture granules with 45% of PE/EVA resin in the hopper, conveying the mixture granules to a reciprocating machine, and carrying out melt processing at 110 ℃ to obtain the multifunctional shielding material.
Comparative example 1
(1) Directly blending 32% of conductive carbon black, 16% of intumescent flame retardant, 9% of auxiliary agent (the types and the contents of the auxiliary agent are respectively 7.2% of white oil, 0.5% of zinc stearate, 1% of ethylene bis stearamide and 0.3% of antioxidant 1010) and 43% of EVA resin in a high-speed mixer for 5 min;
(2) and conveying the blended material to a double screw, and carrying out melt processing at 120 ℃ to obtain the multifunctional shielding material.
Comparative example 2
(1) Weighing 32% of conductive carbon black, 16% of intumescent flame retardant and 9% of auxiliary agent (the types and the contents of the auxiliary agent are respectively 7.2% of white oil, 0.5% of zinc stearate, 1% of ethylene bis stearamide and 0.3% of 1010);
(2) putting the mixture of the filler and the auxiliary agent into a high-speed mixer with far infrared heating, setting the infrared heating power to be 600W, the stirring speed to be 360rpm, and heating, stirring and mixing for 5 min;
(3) and directly conveying the mixed functional filler to a double-screw feeding hopper, uniformly stirring the functional filler and 43% of PE/EVA resin in the hopper, conveying the mixture to a double screw, and performing melt processing at 120 ℃ to obtain the multifunctional shielding material.
Comparative example 3
(1) Weighing 30% of conductive carbon black, 15% of heat-conducting filler and 9% of auxiliary agent (the types and the contents of the auxiliary agent are respectively 7.2% of white oil, 0.5% of zinc stearate, 1% of ethylene bis stearamide, 1% of coupling agent and 0.3% of 1010);
(2) putting the mixture of the filler and the auxiliary agent into a high-speed mixer with electric heating, setting the electric heating power to be 400W, the stirring speed to be 360rpm, and the heating, stirring and mixing time to be 5 min;
(3) conveying the heated and mixed materials to a hopper, extruding the materials by a single screw rod, and preparing functional granules under the bonding action of an auxiliary agent;
(4) and conveying the mixture granules to a double-screw feeding hopper through a single screw, uniformly stirring and mixing the mixture granules with 46% of PE/EVA resin in the hopper, conveying the mixture granules to a reciprocating machine, and carrying out melt processing at 110 ℃ to obtain the multifunctional shielding material.
The prepared multifunctional cable shielding material is blended with a cross-linking agent, then is subjected to cross-linking hot-press molding at 175 ℃, and is subjected to performance test, and the main performances of the obtained examples and comparative examples are shown in table 1.
TABLE 1
| sample/Properties | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile strength MPa | 13.1 | 13.8 | 14.2 | 11.5 | 12.1 | 12.3 |
| Elongation at break% | 235 | 220 | 228 | 226 | 212 | 215 |
| Volume resistivity omega cm | 32 | 28 | 39 | 52 | 45 | 53 |
| Limiting oxygen index% | 28.1 | 28.6 | / | 26.5 | 27.2 | / |
| Coefficient of thermal conductivity W/m.k | / | / | 3.0 | / | / | 2.2 |
It can be seen from the above table that after far infrared heating, high mixing and granulation, the mechanical properties, conductivity and other functionalities of the prepared multifunctional cable shielding material are obviously higher than those of the multifunctional shielding material manufactured by the processes of direct blending, far infrared heating, high temperature, non-granulation, electric heating, high mixing, granulation and the like, and the reason is that the action link of the auxiliary agent is changed by the rapid far infrared heating and high mixing, so that the auxiliary agent is firstly dispersed and combined with the filler, the actual action of the auxiliary agent is more fully exerted by the dispersion of the filler in the melting processing process of the resin, the dispersion of the filler in the matrix and the interface combination effect of the filler and the matrix are obviously improved, and simultaneously, based on the gain brought by the granulation of the functional filler, the functional network of the filler is strengthened, so that the good functionality is ensured and the better mechanical properties are also realized. According to the embodiment and the comparative example of the invention, the technology provided by the invention can prepare the high-performance and multifunctional cable shielding material with more excellent performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (9)
1. A preparation method of a high-performance multifunctional cable shielding material is characterized by comprising the following steps: comprises that
Preparing functional filler and processing aid in proportion, wherein the functional filler comprises conductive filler and other functional fillers;
step two, mixing the conductive filler, the other functional fillers and the processing aid at a high speed, wherein the mixture is heated by far infrared rays in the high-speed mixing process;
step three, extruding and granulating the mixture processed in the step two to obtain functional particles;
and step four, mechanically stirring and uniformly mixing the functional particles and the resin granules, and melting and mixing to obtain the high-performance multifunctional cable shielding material.
2. The method for preparing the high-performance multifunctional cable shielding material according to claim 1, wherein the method comprises the following steps: the conductive filler is selected from at least one of conductive carbon black, conductive graphite, carbon fiber and metal powder; the other functional filler is at least one of flame retardant filler and heat conducting filler.
3. The method for preparing the high-performance multifunctional cable shielding material according to claim 2, wherein the method comprises the following steps: the flame-retardant filler is selected from at least one of red phosphorus compound flame retardant and intumescent compound flame retardant; the heat conductive filler is selected from at least one of alumina, boron nitride and silicon nitride.
4. The method for preparing the high-performance multifunctional cable shielding material according to claim 1, wherein the method comprises the following steps: the processing aid is selected from compounds with molecular weight less than 1500 and melting point less than 170 ℃; the processing aid is at least one selected from an antioxidant, a lubricant, a plasticizer, a coupling agent and a dispersing agent.
5. The method for preparing the high-performance multifunctional cable shielding material according to claim 4, wherein the method comprises the following steps: the antioxidant package is at least one selected from the group consisting of antioxidant 1035, antioxidant 1010, and antioxidant 300: the lubricant is selected from at least one of butyl stearate, zinc stearate, paraffin and ethylene bis stearamide; the plasticizer is selected from at least one of phosphate, phthalate, trimellitate and epoxy glycerol tricarboxylate; the coupling agent is selected from at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
6. The method for preparing the high-performance multifunctional cable shielding material according to claim 1, wherein the method comprises the following steps: the resin is at least one selected from polypropylene, polyethylene, ethylene-vinyl acetate copolymer and polyolefin thermoplastic elastomer.
7. The method for preparing the high-performance multifunctional cable shielding material according to claim 1, wherein the method comprises the following steps: the conductive filler content in the material is 20-40 wt%, the other functional fillers content is 10-30 wt%, the processing aid content is 5-15 wt%, and the resin content is 40-60 wt%.
8. The method for preparing the high-performance multifunctional cable shielding material according to claim 1, wherein the method comprises the following steps: and step two, the power of far infrared radiation heating is 300-800W, the stirring speed of high-speed mixing is 100-500 rpm, and the high-speed mixing time is 1-10 min.
9. The method for preparing the high-performance multifunctional cable shielding material according to claim 1, wherein the method comprises the following steps: in the third step, the mixture is extruded and granulated by a single screw to obtain the functional particles; the high-performance multifunctional cable shielding material in the fourth step is processed by at least one of a double screw, a triple screw and a reciprocating machine.
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| CN104669747A (en) * | 2015-03-02 | 2015-06-03 | 北京东方雨虹防水技术股份有限公司 | Waterproof roll and preparation method thereof |
| CN104710650A (en) * | 2015-03-13 | 2015-06-17 | 瑞安市豪邦橡塑材料有限公司 | Preparation method of environment-friendly chemical mixed additive |
| CN108047535A (en) * | 2017-12-19 | 2018-05-18 | 湖北洋田塑料制品有限公司 | A kind of high-tension cable conductive shield material and preparation method thereof |
| CN113881133A (en) * | 2021-11-18 | 2022-01-04 | 深圳供电局有限公司 | High-voltage cable semiconductive shielding material with conductive carbon black efficiently dispersed and preparation method thereof |
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- 2022-04-02 CN CN202210342553.XA patent/CN114736451A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104669747A (en) * | 2015-03-02 | 2015-06-03 | 北京东方雨虹防水技术股份有限公司 | Waterproof roll and preparation method thereof |
| CN104710650A (en) * | 2015-03-13 | 2015-06-17 | 瑞安市豪邦橡塑材料有限公司 | Preparation method of environment-friendly chemical mixed additive |
| CN108047535A (en) * | 2017-12-19 | 2018-05-18 | 湖北洋田塑料制品有限公司 | A kind of high-tension cable conductive shield material and preparation method thereof |
| CN113881133A (en) * | 2021-11-18 | 2022-01-04 | 深圳供电局有限公司 | High-voltage cable semiconductive shielding material with conductive carbon black efficiently dispersed and preparation method thereof |
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