CN113956602A - Oil-resistant and heat-resistant insulating material and preparation method and application thereof - Google Patents
Oil-resistant and heat-resistant insulating material and preparation method and application thereof Download PDFInfo
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- CN113956602A CN113956602A CN202111172863.3A CN202111172863A CN113956602A CN 113956602 A CN113956602 A CN 113956602A CN 202111172863 A CN202111172863 A CN 202111172863A CN 113956602 A CN113956602 A CN 113956602A
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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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
- H01B3/307—Other macromolecular compounds
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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
- H01B3/44—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 vinyl resins; acrylic resins
- H01B3/441—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 vinyl resins; acrylic resins from alkenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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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
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
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Abstract
The invention discloses an oil-resistant and heat-resistant insulating material as well as a preparation method and application thereof, wherein the preparation raw materials of the insulating material comprise: styrene elastomer, polyethylene and metallocene polyolefin, wherein the styrene mass content of the styrene elastomer is 8-20%. The invention adopts the styrene elastomer with low styrene content and the polyethylene as the base material, the styrene elastomer and the polyethylene can be crosslinked under the irradiation, and the crosslinking degree is obviously increased compared with the prior art, thereby improving the mechanical strength, the heat resistance, the aging resistance and other properties of the insulating material. The metallocene polyolefin can effectively adjust the hardness of the system and improve the toughness of the finished product. And the metallocene polyolefin has shorter branched chains and less quantity, does not participate in the crosslinking reaction, can avoid adverse effects on the crosslinking reaction while improving the toughness of a finished product, and does not need to add mineral oil plasticizers, so that the insulating material has the advantages of high mechanical strength, heat resistance, oil resistance, aging resistance, cracking resistance, low hardness and the like.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an oil-resistant heat-resistant insulating material and a preparation method and application thereof.
Background
At present, most of vehicle-mounted wire insulating materials on the market are irradiation cross-linked polyethylene (XLPE), and although XLPE has the advantages of good insulating property, high mechanical strength, heat resistance, cracking resistance, good processing property and the like, the XLPE is too high in hardness and is not easy to bend in certain narrow spaces of automobiles, and laying is influenced. In the related art, styrene thermoplastic elastomer (TPE) is used as an insulating material, and TPE has the advantages of good mechanical strength, excellent aging resistance, low hardness, convenience in paving and the like, but has the following disadvantages: the temperature resistance grade of the non-oil-resistant, non-crosslinking and non-crosslinking material only reaches 105 ℃ of UL1581, the 125 ℃ or even higher temperature resistance requirement is difficult to achieve, and the non-crosslinking material is easy to cause wire cracking under the action of high temperature and stress.
There are related techniques that use polypropylene blended with SEBS followed by irradiation. Although the compatibility of polypropylene and SEBS is good, the mechanical property of the material can be greatly improved after blending, many researches show that the polypropylene is influenced by lateral methyl of a molecular main chain during irradiation crosslinking, degradation and crosslinking occur simultaneously, the crosslinking rate is quite low, and the ratio of degradation and crosslinking reaction of isotactic PP after gamma-ray irradiation reaches 0.8. Only a few foreign patents have reported that irradiation crosslinking can be achieved with polypropylene of a specific composition, such as polypropylene foam board of Dongli corporation in Japan. In addition, in the related technology, polyethylene and SEBS are blended and then irradiated, although polyethylene is easy to crosslink, styrene of the SEBS is not easy to crosslink, mineral oil such as white mineral oil is used for plasticizing, components influencing crosslinking reaction are introduced when the mineral oil is used, the mineral oil can cause extremely bad influence on materials in the aspects of chemical resistance, heat resistance and the like, and meanwhile, Shore hardness of the product can be changed, oil resistance is poor, and the application in a vehicle-mounted environment is not facilitated.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the oil-resistant and heat-resistant insulating material provided by the invention has the advantages of high mechanical strength, heat resistance, oil resistance, aging resistance, cracking resistance, low hardness and the like.
Meanwhile, the invention also provides a preparation method and application of the insulating material.
Specifically, the invention adopts the following technical scheme:
the first aspect of the invention provides an insulating material, and the raw materials for preparing the insulating material comprise: styrene elastomer, polyethylene and metallocene polyolefin, wherein the styrene mass content of the styrene elastomer is 8-20%.
The insulation material according to the first aspect of the invention has at least the following beneficial effects:
the invention adopts the styrene elastomer with low styrene content and the polyethylene as the base material, the styrene elastomer and the polyethylene can be crosslinked under the irradiation, and the crosslinking degree is obviously increased compared with the prior art, thereby improving the mechanical strength, the heat resistance, the aging resistance and other properties of the insulating material. The metallocene polyolefin can effectively adjust the hardness of the system and improve the toughness of the finished product. And the branched chains in the metallocene polyolefin are shorter and less in number, and do not participate in the crosslinking reaction, so that the toughness of the finished product can be improved, the adverse effect on the crosslinking reaction can be avoided, and the insulating material does not need to be added with a mineral oil plasticizer, so that the damage of mineral oil to the finished product is avoided. Therefore, the insulating material has the advantages of high mechanical strength, heat resistance, oil resistance, aging resistance, cracking resistance, low hardness and the like.
In some embodiments of the invention, the styrenic elastomer has a viscosity of 1000 to 1500cps in a 25% toluene solution at 25 ℃ and a weight average molecular weight of 100000 to 150000.
In some embodiments of the present invention, the styrenic elastomer comprises at least one of styrene-butadiene-styrene block copolymer (SEBS), styrene-butadiene-styrene (SBS), preferably SEBS. In the irradiation crosslinking process, a butadiene (EB) chain segment in the SEBS can also be crosslinked, so that the crosslinking degree of a system is increased, and the tear resistance, the environmental stress cracking resistance, the aging resistance and the oil resistance of the material are improved.
In some embodiments of the invention, the SEBS comprises YH-688, YH506 of the Chinese Yueyanite petrochemical, G1657 of the United states Keteng, and the like.
In some embodiments of the invention, the polyethylene comprises at least one of high density polyethylene, Low Density Polyethylene (LDPE) and linear low density polyethylene, preferably low density polyethylene. The site of occurrence of the crosslinking reaction is preferably selected to be a methyl group or a tertiary carbon atom at the end of a branch, and among these three polyethylenes, LDPE has the most branched structure and is therefore most suitable for use as a crosslinking substrate.
In some embodiments of the invention, the metallocene polyolefin comprises a metallocene polyethylene, preferably a metallocene-catalyzed Linear Low Density Polyethylene (LLDPE) in a metallocene polyethylene. The metallocene polyethylene has a more regular structure and a less shorter branched chain structure, is not easy to generate crosslinking reaction, and can still keep a linear structure after other components are crosslinked, so that the material is ensured not to generate overhigh crosslinking degree, and enough toughness is kept. Metallocene-catalyzed linear low density polyethylenes have good environmental stress crack resistance and tear resistance.
In some embodiments of the invention, the metallocene polyethylene has a melt index of 1 to 7g/10min (230 ℃, 2.16 kg).
In some embodiments of the present invention, the insulation material is prepared from the following raw materials in parts by weight: 25-40 parts of styrene elastomer, 10-20 parts of polyethylene and 5-10 parts of metallocene polyolefin.
In some embodiments of the present invention, the raw material for preparing the insulation material further comprises a cross-linking agent.
In some embodiments of the present invention, the insulation material is prepared from the following raw materials in parts by weight: 25-40 parts of styrene elastomer, 10-20 parts of polyethylene, 5-10 parts of metallocene polyolefin and 5-9 parts of cross-linking agent.
In some embodiments of the present invention, the raw material for preparing the insulation material further includes at least one of a flame retardant, a silicone masterbatch, and an antioxidant, and preferably includes a combination of the flame retardant, the silicone masterbatch, and the antioxidant.
In some embodiments of the present invention, the insulation material is prepared from the following raw materials in parts by weight: 25-40 parts of styrene elastomer, 10-20 parts of polyethylene, 5-10 parts of metallocene polyolefin, 20-30 parts of flame retardant, 1-3 parts of silicone master batch, 5-9 parts of cross-linking agent and 0.1-0.3 part of antioxidant.
In some preferred embodiments of the present invention, the insulation material is prepared from the following raw materials in parts by weight: 30-35 parts of styrene elastomer, 15-20 parts of polyethylene, 6-9 parts of metallocene polyolefin, 25-30 parts of flame retardant, 1.5-2.5 parts of silicone master batch, 5.5-9 parts of cross-linking agent and 0.1-0.3 part of antioxidant.
In some preferred embodiments of the present invention, the insulation material is prepared from the following raw materials in parts by weight: 33-34 parts of styrene elastomer, 18-20 parts of polyethylene, 7-9 parts of metallocene polyolefin, 28-30 parts of flame retardant, 1.5-2.5 parts of silicone master batch, 5.5-6.5 parts of cross-linking agent and 0.1-0.3 part of antioxidant.
In some embodiments of the present invention, the flame retardant comprises at least one of a phosphorus-based flame retardant and a nitrogen-based flame retardant.
In some embodiments of the present invention, the flame retardant comprises a combination of a phosphorus-based flame retardant and a nitrogen-based flame retardant, and the mass ratio of the phosphorus-based flame retardant to the nitrogen-based flame retardant is 1: 0.5 to 2. For example, in the insulating material, the phosphorus flame retardant and the nitrogen flame retardant are 10 to 15 parts by mass independently.
In some embodiments of the invention, the phosphorus-based flame retardant comprises at least one of Aluminum Diethylphosphinate (ADP), aluminum hypophosphite, polyphosphate-based flame retardants. The nitrogen flame retardant comprises at least one of Melamine Cyanurate (MCA) and melamine polyphosphate flame retardants.
In some embodiments of the invention, the silicone masterbatch comprises a polyethylene-based silicone masterbatch and has a siloxane concentration of greater than 50%, such as MBSI-002P of dow corning.
In some embodiments of the invention, the crosslinker is an irradiation crosslinker comprising at least one of TAC, TAIC, TMPTMA, HVA-2, and zinc methacrylate.
In some embodiments of the present invention, the antioxidant may be any antioxidant commonly used in the art, as long as it does not have a side effect on the crosslinking reaction, such as anti-245, anti-1010, etc., without limitation.
The second aspect of the invention provides a preparation method of the insulating material, which comprises the following steps:
mixing the preparation raw materials of the insulating material, and then carrying out melt blending extrusion to obtain colloidal particles;
and carrying out extrusion molding and irradiation on the colloidal particles to obtain the insulating material.
In the preparation process of the insulating material, the extrusion and the crosslinking are separated, the process is simple and visual, the rejection rate is convenient to control, the loss of the extrusion process is less compared with that of a peroxide crosslinking steam continuous vulcanization preparation process, the rejection rate is low, and the economic benefit is better.
In some embodiments of the invention, the mixing method is specifically that the styrene elastomer is stirred for 5-10 minutes at a stirring speed of 300-600 rpm/min, and then other preparation raw materials are added and stirred for 30-60 minutes.
In practical operation, the step of melt blending extrusion can be performed by adopting a double-screw extruder, the double-screw extruder can adopt a co-rotating double-screw extruder with the length-diameter ratio of 40-48, the extrusion temperature is 170-200 ℃, and the rotating speed of a main machine is 250-400 rpm.
And after melt blending and extrusion, storing the obtained colloidal particles in a dark place.
In some embodiments of the invention, the method further comprises a step of drying the colloidal particles before the extrusion, wherein the drying temperature is 60-90 ℃, and the drying time is 0.5-5 h.
In some embodiments of the present invention, the temperature of the extrusion molding is 160 to 185 ℃.
In some embodiments of the invention, the irradiation dose is 10-20 Mard/mm, preferably 15-20 Mard/mm. The irradiation dose should be considered to be the actual thickness, and too high a dose tends to cause material degradation. After irradiation the wire was stored in air at room temperature.
The third aspect of the invention provides a cable, and the raw material for preparing the cable comprises the insulating material. The insulating material has the advantages of high mechanical strength, heat resistance, oil resistance, aging resistance, cracking resistance, low hardness and the like, and can be used for manufacturing various cables, such as vehicle-mounted cables.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the styrene elastomer with low styrene content and the polyethylene are subjected to irradiation after being blended, the crosslinking degree is increased, plasticizers such as white mineral oil and the like are not added, and the damage of mineral oil to a finished product is reduced, so that the irradiated material combines the advantages of the thermoplastic elastomer TPE and the irradiation crosslinked polyethylene, has the advantages of high mechanical strength, heat resistance, oil resistance, aging resistance, cracking resistance, low hardness and the like, and can resist the high temperature of 150 ℃.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples, unless otherwise specified, are available from conventional commercial sources; the processes used, unless otherwise specified, are conventional in the art.
The oil-resistant and high-temperature-resistant cable insulation material comprises the following preparation raw materials in the following table 1.
Table 1 raw material composition of cable insulating material (mass percent)
| Comparative example 1 | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| SEBS | 34 | 34 | 34 | 33 | 32 | 30 |
| LDPE | 28 | 20 | 20 | 20 | 20 | 20 |
| Metallocene LLDPE | 0 | 8 | 8 | 8 | 8 | 8 |
| ADP | 15 | 15 | 15 | 15 | 15 | 15 |
| MCA | 15 | 15 | 15 | 15 | 15 | 15 |
| MBSI-002P | 2 | 2 | 2 | 2 | 2 | 2 |
| TAIC | 5.5 | 5.5 | 5.5 | 6.5 | 7.5 | 9 |
| Reactance 245 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
In the table, SEBS had a styrene content of 13%, a 25% toluene solution viscosity of 1400cps at 25 ℃ and a weight average molecular weight of 140000. Meanwhile, the formula adopts an external calculation method, so the mass percent of all the raw materials in the table is not controlled to be 100 percent.
The cable insulation of each example or comparative example was prepared as follows:
(S1) mixing raw materials: the SEBS is stirred in a mixer with the stirring speed of 500rpm/min for 8 minutes, and then other components are added and stirred for 50 minutes.
(S2) material extrusion: putting the mixed materials into a double-screw extruder for melt blending and extrusion to obtain colloidal particles; the double-screw extruder is a co-rotating double-screw extruder with the length-diameter ratio of 40-48, the extrusion temperature is 170-200 ℃, the rotating speed of a main machine is 250-400 rpm, and the prepared colloidal particles are subjected to light-shielding treatment.
(S3) drying the colloidal particles at 80 ℃ for 2 hours, then carrying out extrusion molding in an extruder by taking a conductor with the outer diameter of 1.7mm as a cable core to form a cable insulating material with the outer diameter of 2.7mm coating the conductor, wherein the temperature during extrusion is about 170 ℃.
(S4) irradiating after extrusion, wherein the irradiation dose is 10-20 Mard/mm. After irradiation, the samples were stored in a ventilated atmosphere at room temperature and tested for performance after one week.
The results of the performance test of the rubber particles and the cable insulation (in which long-term aging was measured according to ISO6722 standard, flame-retardant related properties were measured according to UL62 standard, and other properties were measured according to UL2556 standard) are shown in table 2 below.
TABLE 2 Performance test results for colloidal particles and Cable insulation
Note: the shore hardness, the original tensile strength, and the original breaking strength in table 2 represent test data of the colloidal particles before irradiation, and the band represents test data of the cable insulation after irradiation.
As can be seen from Table 2, the cable insulation material in each example has the advantages of mechanical strength, thermal aging and flame retardance, and all the performances meet the requirements of ISO6722, UL62 and UL2556 standards. As can be seen from the comparative example 1 and the example 1, the tear strength of the material can be greatly improved by adding 8% of LLDPE, and the cracking risk of the material in the use process is effectively avoided. As can be seen from examples 1 and 2, the tensile strength and the hot elongation property can be improved and improved by increasing the irradiation dose, and the elongation at break is slightly reduced; examples 2-5 reflect that as the content of the crosslinking agent TAIC increases, the tensile strength increases first and then decreases, the thermal elongation increases significantly, but the elongation at break decreases.
In addition, in the preparation process, the extrusion and crosslinking are separated, the process is simple and visual, the rejection rate is convenient to control, the loss of the extrusion process is less compared with that of the preparation process of peroxide crosslinking steam continuous vulcanization, the rejection rate is low, and the economic benefit is better.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An insulating material is characterized in that: the preparation raw materials of the insulating material comprise: styrene elastomer, polyethylene and metallocene polyolefin, wherein the styrene mass content of the styrene elastomer is 8-20%.
2. The insulation material according to claim 1, wherein: the styrene elastomer has a viscosity of 1000 to 1500cps in 25% toluene solution at 25 deg.C, and a weight average molecular weight of 100000 to 150000.
3. The insulation material according to claim 2, wherein: the styrene elastomer comprises at least one of styrene-ethylene-butadiene-styrene block copolymer and styrene-butadiene-styrene.
4. The insulation material according to claim 1, wherein: the polyethylene comprises at least one of high density polyethylene, low density polyethylene and linear low density polyethylene, preferably low density polyethylene.
5. The insulation material according to claim 1, wherein: the metallocene polyolefin comprises a metallocene polyethylene.
6. The insulation material according to any one of claims 1 to 5, wherein: the preparation raw materials of the insulating material comprise: 25-40 parts of styrene elastomer, 10-20 parts of polyethylene and 5-10 parts of metallocene polyolefin.
7. The insulation material according to claim 6, wherein: the raw materials for preparing the insulating material also comprise a cross-linking agent; preferably, the raw materials for preparing the insulation material further comprise at least one of a flame retardant, a silicone master batch and an antioxidant, and preferably comprise a combination of the flame retardant, the silicone master batch and the antioxidant.
8. The insulation material according to claim 7, wherein: the insulation material comprises the following raw materials in parts by weight: 25-40 parts of styrene elastomer, 10-20 parts of polyethylene, 5-10 parts of metallocene polyolefin, 20-30 parts of flame retardant, 1-3 parts of silicone master batch, 5-9 parts of cross-linking agent and 0.1-0.3 part of antioxidant.
9. A method for producing an insulating material according to any one of claims 1 to 8, characterized in that: the method comprises the following steps:
mixing the preparation raw materials of the insulating material, and then carrying out melt blending extrusion to obtain colloidal particles;
and carrying out extrusion molding and irradiation on the colloidal particles to obtain the insulating material.
10. A cable, characterized by: the raw material for preparing the cable comprises the insulating material as claimed in any one of claims 1 to 8.
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| CN116218127A (en) * | 2023-05-08 | 2023-06-06 | 广东美的制冷设备有限公司 | Compatilizer and preparation method thereof, alloy material and preparation method thereof, and refrigerator liner |
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