CN103087373B - Radiation crosslinking chloroprene rubber heat-shrink tube and production method thereof - Google Patents

Radiation crosslinking chloroprene rubber heat-shrink tube and production method thereof Download PDF

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CN103087373B
CN103087373B CN201210205497.1A CN201210205497A CN103087373B CN 103087373 B CN103087373 B CN 103087373B CN 201210205497 A CN201210205497 A CN 201210205497A CN 103087373 B CN103087373 B CN 103087373B
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chloroprene rubber
several
carbon black
shrink tube
radiation crosslinking
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CN103087373A (en
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刘卫东
赖兆文
赵源
秦荣勤
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Shenzhen Woer Heat Shrinkable Material Co Ltd
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Shenzhen Woer Heat Shrinkable Material Co Ltd
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Abstract

The present invention discloses a kind of radiation crosslinking chloroprene rubber heat-shrink tube, and it is prepared material and contains by weight: chloroprene rubber 10-100 part; Polyolefine 10-100 part; Compatilizer 0.1-20 part; Fire retardant 10-200 part; Reinforcing filler 0-500 part; Sensitizing agent 0-20 part; Oxidation inhibitor 0.1-20 part.The present invention also provides the production method of radiation crosslinking chloroprene rubber heat-shrink tube, comprising: (1) is blended by above-mentioned materials; (2) by said mixture extruding pelletization, extrude sleeve pipe; (3) by sleeve pipe through rumbatron or cobalt-60 radiosterilize; (4) by the jacket cooling sizing after expansion in (3).Radiation crosslinking chloroprene rubber heat-shrink tube of the present invention has the performance of most oils such as good heatproof, resistance to aviation and ground vehicle fuel, lubricant, hydraulic fluid and solvent, the insulation, particularly oil resistant that are applicable to the various core of a cable contacted with oils require strict occasion.

Description

Radiation crosslinking chloroprene rubber heat-shrink tube and production method thereof
Technical field
The present invention relates to a kind of heat-shrink tube and production method thereof, particularly relate to a kind of radiation crosslinking chloroprene rubber heat-shrink tube and production method thereof.
Background technology
At present, the main raw of heat-shrink tube comprises: (1) polyolefin copolymers or polymkeric substance; (2) one or more materials in rubber type of material or thermoplastic elastic body styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene block copolymer (SIS); (3) other subsidiary material.
But, although existing heat-shrink tube has good flame retardant properties and environmental-protecting performance, but poor-performing in heatproof, oil resistant and solvent resistant, even if or oil resistant is also one or several among resistant to many oil, can not be applicable to heatproof, oil resistant and the solvent-proof places such as automobile, bullet train, military project and space flight industry.
Summary of the invention
The object of the present invention is to provide a kind of can the oils of the resistance to overwhelming majority and solvent and the radiation crosslinking chloroprene rubber heat-shrink tube of heatproof.
For achieving the above object, the invention provides a kind of radiation crosslinking chloroprene rubber heat-shrink tube, it is prepared material and comprises following material by weight: chloroprene rubber 10-100 part; Polyolefine 0-100 part; Compatilizer 0.1-20 part; Fire retardant 10-200 part; Reinforcing filler 0-500 part; Sensitizing agent 0-20 part; Oxidation inhibitor 0.1-20 part.
Described chloroprene rubber is one or several in sulphur adjustment type, non-Sulfur adjustment type.
Described polyolefine is the one or several in acrylic resin, ethylene vinyl acetate (EVA), ethylene ethyl acrylate copolymer (EEA), polyethylene (PE), chlorinatedpolyethylene (CPE), polystyrene (PS).
Described compatilizer comprises acid or anhydride modified PO/EVA, EPR, EPDM, organic-silicon-modified PO, polyphenylene oxide resin, polycaprolactam, SMA, St-MAH-GMA ternary atactic copolymer, anhydride modified SEBS, maleimide copolymer, one or several in peroxidation polymkeric substance.
Described fire retardant can be aluminium hydroxide and/or magnesium hydroxide and/or modified aluminium hydroxide and/or modified magnesium hydroxide and/or high molecular ammonium polyphosphate (APP) and/or phosphate ester flame retardants and/or melamine cyanurate (MCA) and/or melamine pyrophosphate salt (MPP).
Described reinforcing filler is carbon black and mineral filler.
Described carbon black is the one or several of thermo-cracking carbon black, spray method carbon black.
Described mineral filler is the one or several in calcium carbonate, talcum powder, aluminium hydroxide, magnesium hydroxide, white carbon black, potter's clay, kaolin, mica powder, barium sulfate.
Described sensitizing agent is that SA diallyl, toxilic acid diene phenylester, tricyanic acid triolefin phenylester, Ethylene glycol dimethacrylate, hexanodioic acid hexadiene ester, acrylic propyl diester, propyl methacrylate, dichloro-are along the one or several in sub-acid amides of divinyl two etc.
Described oxidation inhibitor is Hinered phenols antioxidant, thioether kind antioxidant, suffocated amine antioxidant, the recombiner of anti copper agent allotment or Hinered phenols antioxidant, thioether kind antioxidant, one or several in suffocated amine antioxidant.Hinered phenols antioxidant can be thiophenols kind antioxidant, triazine Hinered phenols antioxidant, cyanurate Hinered phenols antioxidant etc.Suffocated amine antioxidant can be naphthylamines oxidation inhibitor, pentanoic oxidation inhibitor, to pentanoic oxidation inhibitor, quinoline oxidation inhibitor etc.
The invention has the beneficial effects as follows: radiation crosslinking chloroprene rubber heat-shrink tube of the present invention has the performance of most oils such as good heatproof, resistance to aviation and ground vehicle fuel, lubricant, hydraulic fluid and solvent, the insulation, particularly oil resistant that are applicable to the various core of a cable contacted with oils require strict occasion.
Embodiment
By describing technology contents of the present invention, formula rate in detail, being realized object and effect, be explained in detail below in conjunction with embodiment.
In following examples, if not otherwise specified, every number that relates to all refers to weight part.
Embodiment 1
(1) chloroprene rubber 50 parts, ethylene vinyl acetate (EVA) 50 parts, anhydride modified EVA5 part, carbon black 60 parts, 80 parts, aluminium hydroxide, SA diallyl 2 parts, cyanurate Hinered phenols antioxidant 5 parts is blended, high-speed stirring 10 minutes, temperature of charge controls within the scope of 40 DEG C ~ 60 DEG C;
(2) by said mixture twin screw extruder extruding pelletization at 140 DEG C of temperature; Pellet after above-mentioned granulation is extruded sleeve pipe by single screw extrusion machine at 130 DEG C of temperature;
(3) sleeve pipe then above-mentioned technique obtained is through rumbatron or cobalt-60 radiosterilize, and irradiation dose is 10Mrad, and the sleeve pipe after irradiation expands 2 times with expansion device at 160 DEG C of temperature;
(4) by the jacket cooling sizing after expansion in (3), radiation crosslinking chloroprene rubber heat-shrink tube is obtained.
Refer to table 1, which show the performance test table of the radiation crosslinking chloroprene rubber heat-shrink tube obtained by Application Example 1:
Table 1
Embodiment 2
(1) chloroprene rubber 30 parts, ethylene ethyl acrylate copolymer (EEA) 30 parts, polyethylene (PE) 40 parts, magnesium hydroxide 60 parts, anhydride modified SEBS 6 parts, carbon black 50 parts, Ethylene glycol dimethacrylate 3 parts, thiophenols kind antioxidant 4 parts is blended, high-speed stirring 8-10 minute, temperature of charge controls within the scope of 40 DEG C ~ 60 DEG C;
(2) by said mixture twin screw extruder extruding pelletization at 140 DEG C of temperature; Pellet after above-mentioned granulation is extruded sleeve pipe by single screw extrusion machine at 130 DEG C of temperature;
(3) sleeve pipe then above-mentioned technique obtained is through rumbatron or cobalt-60 radiosterilize, and irradiation dose is 10Mrad, and the sleeve pipe after irradiation expands 2 times with expansion device at 160 DEG C of temperature;
(4) by the jacket cooling sizing after expansion in (3), radiation crosslinking chloroprene rubber heat-shrink tube is obtained.
Refer to table 2, which show the performance test table of the radiation crosslinking chloroprene rubber heat-shrink tube obtained by Application Example 1:
Table 2
Embodiment 3
(1) chloroprene rubber 45 parts, ethylene vinyl acetate (EVA) 25 parts, polyethylene (PE) 35 parts, magnesium hydroxide 40 parts, high molecular ammonium polyphosphate (APP) 25 parts, chlorinatedpolyethylene (CPE) 5 parts, carbon black 30 parts, hexanodioic acid hexadiene ester 3 parts, Hinered phenols antioxidant 10103 parts, suffocated amine antioxidant 1682.5 parts is blended, high-speed stirring 8-10 minute, temperature of charge controls within the scope of 40 DEG C ~ 60 DEG C;
(2) by said mixture twin screw extruder extruding pelletization at 125-140 DEG C of temperature; Pellet after above-mentioned granulation is extruded sleeve pipe by single screw extrusion machine at 130 DEG C of temperature;
(3) sleeve pipe then above-mentioned technique obtained is through rumbatron or cobalt-60 radiosterilize, and irradiation dose is 8Mrad, and the sleeve pipe after irradiation expands 2.5 times with expansion device at 110-150 DEG C of temperature;
(4) by the jacket cooling sizing after expansion in (3), radiation crosslinking chloroprene rubber heat-shrink tube is obtained.
Refer to table 3, which show the performance test table of the radiation crosslinking chloroprene rubber heat-shrink tube obtained by Application Example 1:
Table 3
Embodiment 4
(1) be that Tyox B (anti-oxidant DLTP) 3.5 parts is blended by chloroprene rubber 30 parts, ethylene vinyl acetate (EVA) 60 parts, polyethylene (PE) 10 parts, magnesium hydroxide 30 parts, melamine cyanurate (MCA) 30 parts, St-MAH-GMA ternary atactic copolymer 4 parts, carbon black 80 parts, hexanodioic acid hexadiene ester 3 parts, Hinered phenols antioxidant 10103 parts, oxidation inhibitor, high-speed stirring 8-10 minute, temperature of charge controls within the scope of 40 DEG C ~ 60 DEG C;
(2) by said mixture twin screw extruder extruding pelletization at 125-140 DEG C of temperature; Pellet after above-mentioned granulation is extruded sleeve pipe by single screw extrusion machine at 130 DEG C of temperature;
(3) sleeve pipe then above-mentioned technique obtained is through rumbatron or cobalt-60 radiosterilize, and irradiation dose is 8Mrad, and the sleeve pipe after irradiation expands 2.5 times with expansion device at 110-150 DEG C of temperature;
(4) by the jacket cooling sizing after expansion in (3), radiation crosslinking chloroprene rubber heat-shrink tube is obtained.
Refer to table 4, which show the performance test table of the radiation crosslinking chloroprene rubber heat-shrink tube obtained by Application Example 1:
Table 4
In sum, radiation crosslinking chloroprene rubber heat-shrink tube of the present invention has the performance of most oils such as good heatproof, resistance to aviation and ground vehicle fuel, lubricant, hydraulic fluid and solvent, the insulation, particularly oil resistant that are applicable to the various core of a cable contacted with oils require strict occasion.
The present invention is not limited to above-mentioned embodiment, and those skilled in the art also can make multiple change accordingly, but to be anyly equal to the present invention or similar change all should be encompassed in the scope of the claims in the present invention.

Claims (2)

1. a radiation crosslinking chloroprene rubber heat-shrink tube, is characterized in that: it is prepared material and comprises following material by weight: chloroprene rubber 10-100 part, and described chloroprene rubber is one or several in sulphur adjustment type, non-Sulfur adjustment type; Polyolefine 10-100 part, described polyolefine is the one or several in acrylic resin, ethylene vinyl acetate (EVA), ethylene ethyl acrylate copolymer (EEA), polyethylene (PE), chlorinatedpolyethylene (CPE), polystyrene (PS); Compatilizer 0.1-20 part, described compatilizer comprises acid or anhydride modified PO/EVA, EPR, EPDM, organic-silicon-modified PO, polyphenylene oxide resin, polycaprolactam, SMA, St-MAH-GMA ternary atactic copolymer, anhydride modified SEBS, maleimide copolymer, one or several in peroxidation polymkeric substance; Fire retardant 10-200 part; Reinforcing filler 0-500 part, described reinforcing filler is carbon black and mineral filler, described carbon black is the one or several of thermo-cracking carbon black, spray method carbon black, and described mineral filler is the one or several in calcium carbonate, talcum powder, aluminium hydroxide, magnesium hydroxide, white carbon black, potter's clay, kaolin, mica powder, barium sulfate; Sensitizing agent 0-20 part, described sensitizing agent is that SA diallyl, toxilic acid diene phenylester, tricyanic acid triolefin phenylester, Ethylene glycol dimethacrylate, hexanodioic acid hexadiene ester, propyl acrylate, propyl methacrylate, dichloro-are along the one or several in the sub-acid amides of divinyl two; Oxidation inhibitor 0.1-20 part, described oxidation inhibitor is Hinered phenols antioxidant, thioether kind antioxidant, suffocated amine antioxidant, the recombiner of anti copper agent allotment or Hinered phenols antioxidant, thioether kind antioxidant, one or several in suffocated amine antioxidant.
2. a production method for radiation crosslinking chloroprene rubber heat-shrink tube as claimed in claim 1, is characterized in that: the production method of described radiation crosslinking chloroprene rubber heat-shrink tube comprises the following steps:
(1) chloroprene rubber 10-100 part, polyolefine 10-100 part, compatilizer 0.1-20 part, fire retardant 10-200 part, reinforcing filler 0-500 part, sensitizing agent 0-20 part, oxidation inhibitor 0.1-20 part is blended, high-speed stirring 5-10 minute, temperature of charge controls within the scope of 20 DEG C ~ 80 DEG C; Wherein, described chloroprene rubber is one or several in sulphur adjustment type, non-Sulfur adjustment type; Described polyolefine is the one or several in acrylic resin, ethylene vinyl acetate (EVA), ethylene ethyl acrylate copolymer (EEA), polyethylene (PE), chlorinatedpolyethylene (CPE), polystyrene (PS); Described compatilizer comprises acid or anhydride modified PO/EVA, EPR, EPDM, organic-silicon-modified PO, polyphenylene oxide resin, polycaprolactam, SMA, St-MAH-GMA ternary atactic copolymer, anhydride modified SEBS, maleimide copolymer, one or several in peroxidation polymkeric substance; Described reinforcing filler is carbon black and mineral filler, described carbon black is the one or several of thermo-cracking carbon black, spray method carbon black, and described mineral filler is the one or several in calcium carbonate, talcum powder, aluminium hydroxide, magnesium hydroxide, white carbon black, potter's clay, kaolin, mica powder, barium sulfate; Described sensitizing agent is that SA diallyl, toxilic acid diene phenylester, tricyanic acid triolefin phenylester, Ethylene glycol dimethacrylate, hexanodioic acid hexadiene ester, propyl acrylate, propyl methacrylate, dichloro-are along the one or several in the sub-acid amides of divinyl two; Oxidation inhibitor 0.1-20 part, described oxidation inhibitor is Hinered phenols antioxidant, thioether kind antioxidant, suffocated amine antioxidant, the recombiner of anti copper agent allotment or Hinered phenols antioxidant, thioether kind antioxidant, one or several in suffocated amine antioxidant;
(2) by said mixture screw extrusion press extruding pelletization at 100-160 DEG C of temperature; Pellet after above-mentioned granulation is extruded sleeve pipe by screw extrusion press at 100-160 DEG C of temperature;
(3) sleeve pipe then above-mentioned technique obtained is through rumbatron or cobalt-60 radiosterilize, and irradiation dose is 4-20Mrad, and the sleeve pipe after irradiation expands 1-3 doubly with expansion device at 100-180 DEG C of temperature;
(4) by the jacket cooling sizing after expansion in (3), radiation crosslinking chloroprene rubber heat-shrink tube is obtained.
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