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CN102936369B - Silane self-crosslinked polyolefin flexible insulation cable material and preparation method thereof - Google Patents

Silane self-crosslinked polyolefin flexible insulation cable material and preparation method thereof Download PDF

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CN102936369B
CN102936369B CN201210488851.6A CN201210488851A CN102936369B CN 102936369 B CN102936369 B CN 102936369B CN 201210488851 A CN201210488851 A CN 201210488851A CN 102936369 B CN102936369 B CN 102936369B
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grafting
ethylene
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oxidation inhibitor
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CN102936369A (en
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张丽本
栾珊珊
王兴宁
陈敏
顾金云
李小刚
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JIANGSU DEWEI ADVANCED MATERIALS CO Ltd
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JIANGSU DEWEI ADVANCED MATERIALS CO Ltd
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Abstract

The invention relates to a silane self-crosslinked polyolefin flexible insulation cable material and a preparation method thereof. The cable material comprises a grafting component A and a catalytic component B in a weight ratio of 95:(4-6), wherein the grafting component A comprises the following components in parts by weight: 10-35 parts of high-strength polyethylene resin, 25-55 parts of ethylene-octylene copolymer, 20-65 parts of ethylene propylene diene monomer, 0.1-4 parts of 3-aminopropyltrimethoxysilane, 1-6 parts of silane crosslinking agent, 0.5-1.5 parts of grafting initiator, 0.2-2 parts of lubricant and 0.1-5 parts of first antioxidant; and the catalytic component B comprises the following components in parts by weight: 100 parts of ethylene-vinyl acetate copolymer and/or ethylene-octylene copolymer, 1-5 parts of second antioxidant, 1-10 parts of antioxidant and 1-8 parts of crosslinking catalyst. The cable material provided by the invention has the advantages of excellent temperature tolerance, high softness and high oil resistance, and is applicable to the field of electromechanical devices.

Description

A kind of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS and preparation method thereof
Technical field
The present invention relates to a kind of polyolefin insulation material that can be applicable to electromechanical equipment field, be specifically related to a kind of silane self crosslinking polyolefin flexible insulation material, its preparation method and by its prepared cable.
Background technology
At present along with particularly carrying forward vigorously of upgrade of rural power grids of national grid, the quickening that urbanization is marched into the arena, and being gradually improved of urban rail transit construction, increasing by the demand of high temperature resistant soft polyolefin insulation material to electromechanical equipment, but this type of Insulation Material is all mainly irradiation crosslinked polyolefin insulating material or needs poach could realize crosslinked silane cross-linked polyolefin Insulation Material at present, all has the problem that cost is higher.
Chinese invention patent application 200810023270.9 discloses a kind of boiling-free silicane cross-linking polyolefin composition.Although the disclosed CABLE MATERIALS of this patent has realized the feature of self-crosslinking, this Insulation Material only can meet life-time service under lesser temps (90 DEG C), and does not possess flexible nature, thereby cannot be used for electromechanical equipment.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS that can be applicable to electromechanical equipment is provided.
The present invention also will provide a kind of preparation method of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS simultaneously.
For solving the problems of the technologies described above, a kind of technical scheme that the present invention takes is as follows:
A kind of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, it comprises that weight proportion is grafting A component and the catalysis B component of 95:4 ~ 6, wherein:
In grafting A component, each component and each component proportion are: high-strength polyethylene resin 10 ~ 35 weight parts, ethylene-octene copolymer 25 ~ 55 weight parts, terpolymer EP rubber 20 ~ 65 weight parts, 3-aminopropyl trimethoxysilane 0.1 ~ 4 weight part, silane crosslinker 1 ~ 6 weight part, grafting initiator 0.5 ~ 1.5 weight part, lubricant 0.2 ~ 2 weight part, the first oxidation inhibitor 0.1 ~ 5 weight part, wherein: high-strength polyethylene resin, ethylene-octene copolymer and terpolymer EP rubber three's total amount is 100 parts, the melting index of described high-strength polyethylene resin is 0.1g/10min ~ 3.5g/10min, and tensile strength is more than or equal to 35MPa, the first described oxidation inhibitor is to be selected from one or more in antioxidant 1010, irgasfos 168 and antioxidant 300,
In catalysis B component, each component and each component proportion are: ethylene-vinyl acetate copolymer or ethylene-octene copolymer or the mixture of the two 100 weight parts; The second oxidation inhibitor 1 ~ 5 weight part; The 3rd oxidation inhibitor 1 ~ 10 weight part; And 1 ~ 8 part of crosslinking catalyst, wherein, the second oxidation inhibitor is that oxidation inhibitor 1024, the three oxidation inhibitor are to be selected from one or more of phenolic antioxidant, amine antioxidants, thiobisphenol kind antioxidant and phosphite ester kind antioxidant.
According to further embodiment of the present invention:
Silane crosslinker in described grafting A component can and be preferably and is selected from one or more in vinyltrimethoxy silane, vinyltriethoxysilane, γ-aminopropyl triethoxysilane and diethylenetriamine base propyl trimethoxy silicane.
Lubricant in described grafting A component can and be preferably and is selected from one or more in fluorine-containing rheological agent (PPA), silicone master batch and stearate.Wherein, stearate can be for being selected from one or more the combination in Zinic stearas, Magnesium Stearate and barium stearate.
Grafting initiator in described grafting A component can and be preferably dicumyl peroxide (DCP) or 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane (DBPH) or the mixture of the two.
Preferably, the high-strength polyethylene resin in described grafting A component is metallocene PE and/or bimodal polyethylene.
Crosslinking catalyst in described catalysis B component can be organic tin catalyzer or ester class catalyzer.For example, crosslinking catalyst can be for being selected from one or more in dibutyl tin laurate, two lauric acid two fourth tin octylates and cyanacrylate.
Preferably, in catalysis B component, contain ethylene-vinyl acetate copolymer and ethylene-octene copolymer, the weight ratio of the two is 1:0.4 ~ 3 simultaneously.
Preferably, the weight ratio of described grafting A component and catalysis B component is 95:5.
According to the present invention, the ethylene-octene copolymer using in grafting A component preferably possesses following features: melting index is 1 ~ 2g/10min; Ethylene-octene copolymer in catalysis B component preferably possesses following features: melting index is 5 ~ 10g/10min.
The another technical scheme that the present invention takes is: a kind of preparation method of above-mentioned silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, it comprises the steps:
(1) prepare grafting A component: according to formula rate, silane crosslinker, grafting initiator, the first oxidation inhibitor, 3-aminopropyl trimethoxysilane are mixed, obtain crosslinked mixed solution; By formula, high-strength polyethylene resin, ethylene-octene copolymer, terpolymer EP rubber, mix lubricant is even, add in BUSS mixing roll hopper, claim accurately to weigh crosslinked mixed solution with liquid enters in BUSS mixing roll by lance injected simultaneously, through BUSS machine mixing granulator, water extracter dehydration, drying machine is dried to obtain grafting A component;
(2), preparation catalysis B component: ethylene-vinyl acetate copolymer or ethylene-octene copolymer or the mixture of the two, the second oxidation inhibitor, the 3rd oxidation inhibitor and crosslinking catalyst are mixed by formula, extrude through twin screw extruder, water stretching and granulation, the dry catalysis B component that makes;
(3), step (1) gained grafting A component and step (2) gained catalysis B component obtained to described silane self crosslinking polyolefin flexible insulation CABLE MATERIALS by weight aluminum-plastic packaged.
Further, in rapid (1), the temperature setting of BUSS mixing roll is set to: 155 DEG C ~ 185 DEG C of compression sections, 195 DEG C ~ 215 DEG C of homogenizing zones, 130 DEG C ~ 145 DEG C of head temperatures.
In step (2), feeding section, compression section, homogenizing zone and the head temperature of twin screw extruder is followed successively by 120 DEG C ~ 130 DEG C, 135 DEG C ~ 155 DEG C, 160 DEG C ~ 175 DEG C and 165 DEG C ~ 185 DEG C.
In the present invention, all described raw materials all can be by being purchased and/or taking known means to prepare, and meet the requirement of stdn chemical product.
The present invention also relates to a kind of silane self crosslinking polyolefin flexible insulation cable, and it is to be 95:4 ~ 6 mix after, through cable forcing machine to extrude gained with above-mentioned catalysis B component according to weight proportion by above-mentioned grafting A component.
The invention still further relates to above-mentioned silane self crosslinking polyolefin flexible insulation cable application in the purposes in electromechanical equipment field.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
Silane self crosslinking polyolefin flexible insulation CABLE MATERIALS provided by the invention is a kind of novel silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, it has superior heat resistance (125 DEG C), aging resistance, softness, oil resistance, and processing characteristics excellence, cost is low, can be applicable to electromechanical equipment field.
Compared with the preparation method of the preparation method of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS provided by the invention and traditional silane cross-linked polyolefin Insulation Material, the graft(ing) degree and the generation that prevents precrosslink that have effectively ensured material, gained CABLE MATERIALS has more excellent heat resistance and softness.And have for compared with the cable product in electromechanical equipment field, preparation of the present invention is simpler, cost is lower.
Embodiment
The raw material adopting in following examples is commercially available standard industry product.
Embodiment 1
The present embodiment provides a kind of preparation method of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, and the raw material of employing and consumption are referring to table 1, wherein:
High tensile polyvinyl resin is that Borealis produces bimodal polyethylene, the trade mark: FB2230, and melting index is 0.2g/10min; The mooney viscosity of terpolymer EP rubber is 25, and propylene content is 25wt%; With ethylene-octene copolymer, Shore A hardness is 75; The first oxidation inhibitor is antioxidant 300, and lubricant is PPA, and grafting initiator is DCP.
The vinyl acetate content of ethylene-vinyl acetate copolymer is 28wt%; Silane crosslinker is vinyltrimethoxy silane; Antioxidant 1010 and irgasfos 168 that the 3rd antioxidant packages is 1:1 containing weight ratio;
Crosslinking catalyst is dibutyl tin laurate.
The preparation method of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS comprises the steps:
(1) by silane crosslinker, grafting initiator, antioxidant 300,3-aminopropyl trimethoxysilane, be mixed into crosslinked mixed solution; Then high-strength polyethylene resin, ethylene-octene copolymer (melting index is 2.0g/10min), terpolymer EP rubber, mix lubricant are evenly added in BUSS mixing roll hopper, claim accurately to weigh crosslinked mixed solution with liquid enters in BUSS mixing roll by lance injected simultaneously, through BUSS machine mixing granulator, water extracter dehydration, drying machine is dried to obtain grafting A component.
(2) ethylene-vinyl acetate copolymer and ethylene-octene copolymer (melting index is 8.0g/10min), oxidation inhibitor 1024, the 3rd oxidation inhibitor and crosslinking catalyst are mixed by proportioning, through twin-screw extrusion, water stretching and granulation, make catalysis B component, wherein: in step (2), feeding section, compression section, homogenizing zone and the head temperature of twin screw extruder are followed successively by 120 ~ 130 DEG C, 135 ~ 155 DEG C, 160 ~ 175 DEG C and 165 ~ 185 DEG C.
(3) by step (1) gained grafting A component and step (2) gained catalysis B component 95:5 proportioning packaging by weight ratio, to obtain final product.
Embodiment 2
The present embodiment provides a kind of preparation method of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, and the raw material that it adopts and consumption are referring to table 1, and the raw material outside high-strength polyethylene resin and grafting initiator is all identical with embodiment 1.
In this example, selected high-strength polyethylene resin is that Exxon Corporation produces the metallocene PE trade mark: 3518CB, its melting index is 3.5g/10min.
In this example, grafting initiator is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane (DBPH).
The preparation process of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS is with embodiment 1.
Embodiment 3
The present embodiment provides a kind of preparation method of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, and the raw material that it adopts and consumption are referring to table 1, and the raw material outside silane crosslinker, lubricant and the 3rd oxidation inhibitor is all identical with embodiment 1.
In this example, silane crosslinker is vinyltriethoxysilane; Lubricant is silicone master batch; Antioxidant 1010 and irgasfos 168 that the 3rd antioxidant packages is 2:1 containing weight ratio.
The preparation process of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS is with embodiment 1.
Embodiment 4
The present embodiment provides a kind of preparation method of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, and the raw material that it adopts and consumption are referring to table 1, and the raw material outside high-strength polyethylene resin and silane crosslinker is all identical with embodiment 1.
In this example, selected high-strength polyethylene resin is that Exxon Corporation produces the metallocene PE trade mark: 3518CB, and its melting index is 3.5g/10min; Silane crosslinker is vinyltriethoxysilane.
The preparation process of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS is with embodiment 1.
Embodiment 5
The present embodiment provides a kind of preparation method of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, and the raw material that it adopts and consumption are referring to table 1, and the raw material outside grafting initiator and crosslinking catalyst agent is all identical with embodiment 1.
In this example, grafting initiator is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane (DBPH); Crosslinking catalyst stannous octoate.
The preparation process of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS is with embodiment 1.
Comparative example 1
This comparative example provides a kind of preparation method of 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, and the raw material that it adopts and consumption are completely with embodiment 1, and different, it is prepared as follows:
(1) terpolymer EP rubber, ethylene-octene copolymer, polyethylene, silane crosslinker, grafting initiator, oxidation inhibitor, lubricant and anti-precrosslinker are evenly mixed by proportioning, through the granulation of reciprocating BUSS machine forcing machine fusion-grafting, dry, obtain grafting A component
(2) ethylene-vinyl acetate copolymer and ethylene-octene copolymer, oxidation inhibitor 1024, the second oxidation inhibitor and crosslinking catalyst are mixed by proportioning, through twin screw extruder extruding pelletization, make catalysis B component.
(3) step (1) gained grafting A component and step (2) gained catalysis B component are packed by proportioning, be 125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS.
The raw material composition of table 1 embodiment 1 ~ 5
125 DEG C of silane self crosslinking polyolefin flexible insulation CABLE MATERIALS prepared by embodiment 1 ~ 5 and comparative example 1 are made test sample (1mm thickness sample, at 25 DEG C, placement 120h naturally under 65% ambient temperature conditions), and properties is tested.Result is referring to table 2.For ease of relatively, also in table 2, list the desired value of this material company standard defined.
The performance of the silane self crosslinking polyolefin flexible insulation CABLE MATERIALS of table 2 embodiment 1 ~ 5 and comparative example 1
Above the present invention is described in detail; its object is to allow the personage who is familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; and the invention is not restricted to the embodiments described; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.

Claims (8)

1. a silane self crosslinking polyolefin flexible insulation CABLE MATERIALS, is characterized in that: it comprises that weight proportion is grafting A component and the catalysis B component of 95:4 ~ 6, wherein:
In grafting A component, each component and each component proportion are: high-strength polyethylene resin 10 ~ 35 weight parts, ethylene-octene copolymer 25 ~ 55 weight parts, terpolymer EP rubber 20 ~ 65 weight parts, 3-aminopropyl trimethoxysilane 0.1 ~ 4 weight part, silane crosslinker 1 ~ 6 weight part, grafting initiator 0.5 ~ 1.5 weight part, lubricant 0.2 ~ 2 weight part, the first oxidation inhibitor 0.1 ~ 5 weight part, wherein: high-strength polyethylene resin, ethylene-octene copolymer and terpolymer EP rubber three's total amount is 100 parts, the melting index of described high-strength polyethylene resin is 0.1g/10min ~ 3.5g/10min, and tensile strength is more than or equal to 35MPa, described high-strength polyethylene resin is metallocene PE and/or bimodal polyethylene, the first described oxidation inhibitor is to be selected from one or more in antioxidant 1010, irgasfos 168 and antioxidant 300, described silane crosslinker is to be selected from one or more in vinyltrimethoxy silane, vinyltriethoxysilane, γ-aminopropyl triethoxysilane and diethylenetriamine base propyl trimethoxy silicane,
In catalysis B component, each component and each component proportion are: ethylene-vinyl acetate copolymer or ethylene-octene copolymer or the mixture of the two 100 weight parts; The second oxidation inhibitor 1 ~ 5 weight part; The 3rd oxidation inhibitor 1 ~ 10 weight part; And 1 ~ 8 part of crosslinking catalyst, wherein, the second oxidation inhibitor is that oxidation inhibitor 1024, the three oxidation inhibitor are to be selected from one or more of phenolic antioxidant, amine antioxidants, thiobisphenol kind antioxidant and phosphite ester kind antioxidant;
Described silane self crosslinking polyolefin flexible insulation CABLE MATERIALS makes as follows:
(1) prepare grafting A component: according to formula rate, silane crosslinker, grafting initiator, the first oxidation inhibitor, 3-aminopropyl trimethoxysilane are mixed, obtain crosslinked mixed solution; By formula, high-strength polyethylene resin, ethylene-octene copolymer, terpolymer EP rubber, mix lubricant is even, add in BUSS mixing roll hopper, claim accurately to weigh crosslinked mixed solution with liquid enters in BUSS mixing roll by lance injected simultaneously, through BUSS machine mixing granulator, water extracter dehydration, drying machine is dried to obtain grafting A component;
(2), preparation catalysis B component: ethylene-vinyl acetate copolymer or ethylene-octene copolymer or the mixture of the two, the second oxidation inhibitor, the 3rd oxidation inhibitor and crosslinking catalyst are mixed by formula, extrude through twin screw extruder, water stretching and granulation, the dry catalysis B component that makes;
(3), step (1) gained grafting A component and step (2) gained catalysis B component obtained to described silane self crosslinking polyolefin flexible insulation CABLE MATERIALS by weight aluminum-plastic packaged.
2. silane self crosslinking polyolefin flexible insulation CABLE MATERIALS according to claim 1, is characterized in that: the lubricant in described grafting A component is to be selected from one or more in fluorine-containing rheological agent, silicone master batch and stearate.
3. silane self crosslinking polyolefin flexible insulation CABLE MATERIALS according to claim 1, it is characterized in that: the grafting initiator in described grafting A component is dicumyl peroxide or 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane or the mixture of the two.
4. silane self crosslinking polyolefin flexible insulation CABLE MATERIALS according to claim 1, is characterized in that: the crosslinking catalyst in described catalysis B component is to be selected from a kind of in dibutyl tin laurate and cyanacrylate or two kinds.
5. a preparation method for the silane self crosslinking polyolefin flexible insulation CABLE MATERIALS as described in any one claim in claim 1 to 4, is characterized in that: comprise the steps:
(1) prepare grafting A component: according to formula rate, silane crosslinker, grafting initiator, the first oxidation inhibitor, 3-aminopropyl trimethoxysilane are mixed, obtain crosslinked mixed solution; By formula, high-strength polyethylene resin, ethylene-octene copolymer, terpolymer EP rubber, mix lubricant is even, add in BUSS mixing roll hopper, claim accurately to weigh crosslinked mixed solution with liquid enters in BUSS mixing roll by lance injected simultaneously, through BUSS machine mixing granulator, water extracter dehydration, drying machine is dried to obtain grafting A component;
(2), preparation catalysis B component: ethylene-vinyl acetate copolymer or ethylene-octene copolymer or the mixture of the two, the second oxidation inhibitor, the 3rd oxidation inhibitor and crosslinking catalyst are mixed by formula, extrude through twin screw extruder, water stretching and granulation, the dry catalysis B component that makes;
(3), step (1) gained grafting A component and step (2) gained catalysis B component obtained to described silane self crosslinking polyolefin flexible insulation CABLE MATERIALS by weight aluminum-plastic packaged.
6. preparation method according to claim 5, is characterized in that: in step (1), the temperature setting of BUSS mixing roll is set to: 155 DEG C ~ 185 DEG C of compression sections, 195 DEG C ~ 215 DEG C of homogenizing zones, 130 DEG C ~ 145 DEG C of head temperatures.
7. preparation method according to claim 5, it is characterized in that: in step (2), feeding section, compression section, homogenizing zone and the head temperature of twin screw extruder is followed successively by 120 DEG C ~ 130 DEG C, 135 DEG C ~ 155 DEG C, 160 DEG C ~ 175 DEG C and 165 DEG C ~ 185 DEG C.
8. a silane self crosslinking polyolefin flexible insulation cable, it is characterized in that: it is to be 95:4 ~ 6 mix after, through cable forcing machine to extrude gained with the catalysis B component described in any one claim in claim 1 to 4 according to weight proportion by the grafting A component described in any one claim in claim 1 to 4.
CN201210488851.6A 2012-11-26 2012-11-26 Silane self-crosslinked polyolefin flexible insulation cable material and preparation method thereof Active CN102936369B (en)

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