CN101456986A - Special material for silane cross-linked polyethylene cable with ultrafine rigid particles and preparation technology thereof - Google Patents
Special material for silane cross-linked polyethylene cable with ultrafine rigid particles and preparation technology thereof Download PDFInfo
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- CN101456986A CN101456986A CNA2007101508641A CN200710150864A CN101456986A CN 101456986 A CN101456986 A CN 101456986A CN A2007101508641 A CNA2007101508641 A CN A2007101508641A CN 200710150864 A CN200710150864 A CN 200710150864A CN 101456986 A CN101456986 A CN 101456986A
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Abstract
The invention relates to power cable silane cross bond in polyenthylene insulation plastics, particularly to special materials for ultra fine rigid particle padding silane cross bonding polyethylene cabel and a preparation method thereof. The weight ratio is 100 polyethylene resin with low density, 1 to 5 silane, 0.1 to 10 peroxide evocating agent, 0.1 to 10 silanol condensation catalyst, 0.12 to 10 antioxidant, 1 to 30 ultra fine rigid particle, and 0.1 to 5 resin acceptor. Under a regulated technology, the material pellets and mixed and then cable processing and forming are carried out. Then the n products are socked in hot water or steam for cross bonding. The invention aims at using dispersing technology owned by our company to solve twice reunion phenomenon of padding ultra fine rigid particles, to fully bring the characteristics of strengthening and kneading strengthening of the ultra fine rigid particle into play, to combine organically the ultra fine rigid particle padding and silane cross bonding, and to provide a preparation method reducing cost under the premise of guaranteeing special materials of silane cross bonding polyethylene cable.
Description
Technical field
The present invention relates to technical field of polymer materials, especially silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound and technology of preparing thereof.
Background technology
Domestic most of low-voltage cables (line) coat with polyvinyl chloride at present, can emit choke damp and smog when short circuit or fire, jeopardize people's life.Crosslinked polyethylene have good heat resistance, carrying capacity by force, do not melt, corrosion-resistant, advantages such as mechanical property is high, electrical property is excellent, not leaded class stablizer, replace traditional igelite gradually, be widely used in producing aspects such as power cable, umbilical cable, overhead line and telecommunication cable.
Polyly crosslinkedly can adopt chemically crosslinked, cross-linking radiation and three kinds of methods of crosslinked with silicane.Wherein: chemically crosslinked is to make linking agent with organo-peroxide, because required temperature, pressure requires comparatively harshness in the cross-linking process, has brought technologic difficulty; Cross-linking radiation is that to utilize high-energy radiation to carry out crosslinked, and its shortcoming is that equipment manufacturing cost height, safety precaution complexity and high-energy radiation are big to the material property damage; The above relatively two kinds of cross-linking methods of crosslinked with silicane have characteristics such as less investment, adaptability is strong, technology is easy.The low-voltage crosslinked Polyethylene insulated cable market of 150V～1.5kV is mainly captured by organosilane cross-linked poly-ethylene cable both at home and abroad at present.
At present along with constantly the raising up of oil price, domestic resin raw material price is also soaring step by step, and various plasthetics costs improve.So reduce production costs when how to guarantee product performance, become the problem that the parties concerned press for solution.
Summary of the invention
The objective of the invention is to, utilize the exclusive dispersion technology of my company to solve the secondary agglomeration phenomenon of filling ultra-fine rigid particles, give full play to ultra-fine rigid particles and strengthen toughness reinforcing characteristic, ultra-fine rigid-particle filled and crosslinked with silicane is organically combined, providing a kind of can reduce cost under the prerequisite of guaranteed performance, uses the preparation method of silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound.
The present invention is achieved through the following technical solutions:
80～110 parts of ldpe resins;
0.5～5 part in silane;
0.1～10 part of peroxide initiator;
0.1～10 part of silanol condensation catalyst;
0.1～10 part of antioxidant;
1～30 part of ultra-fine rigid particles;
0.05～5 part of coupling agent.
Its technology of preparing may further comprise the steps:
(1) superfine powder of preparation modification:
Superfine powder is put into the high mixer high speed to mix, temperature begins dehumidifier when reaching 80 ℃～90 ℃, after temperature reaches 105 ℃～150 ℃, add coupling agent and mix stirring 5～10min, then the compound in the high mixer is put in the cold mixer and cooled off, be cooled to the superfine powder that discharging after 30 ℃～50 ℃ obtains modification;
(2) the catalysis masterbatch of preparation silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound:
With ldpe resin, superfine powder, catalyzer, antioxidant is put into cold mixer, emit material and extruding pelletization on twin screw extruder after mixing stirring 2～10min, one district's temperature is 120～150 ℃ from the spout to the die head, 140～170 ℃ of two district's temperature, 150～180 ℃ of three district's temperature, 150～180 ℃ of four district's temperature, 150～180 ℃ of five district's temperature, 160～190 ℃ of six district's temperature, 160～190 ℃ of seven district's temperature, 170～200 ℃ of eight district's temperature, 170～200 ℃ of nine district's temperature, residence time are 0.5～2min, and engine speed is 200～600r/min, discharging, extrude the back pelletizing, cooling, drying, the catalysis masterbatch of silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound.
(3) preparation silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound:
Catalysis masterbatch, the ldpe resin of silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound is dry in Vacuumdrier, 70～90 ℃ of drying temperatures, time of drying 5～20min, catalysis masterbatch, the ldpe resin of dried silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound are put into cold mixer, add linking agent and initiator, mix stir behind 2～10min discharging silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound finished product.
And described ldpe resin melt flow rate (MFR) is 0.5～3.0g/10min (190 ℃ record under the 2.16kg condition), and density is 0.915～0.928g/cm
3
And described silane general formula is RSi (OR ')
3Wherein R is undersaturated olefin group, R ' is generally methyl or ethyl, can be choosing any one kind of them or several mixtures in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxyethoxy) silane or the methacryloxypropyl triethoxyl silane.
And described initiator is a peroxide initiator, is selected from dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5 di-tert-butyl peroxide or benzoyl peroxide, and the described decomposition of initiator transformation period is below 5 minutes.
And described silanol condensation catalyst is selected from one or more the mixture in dibutyl tin laurate, two sad dibutyl tins, the dibutyltin diacetate.
And, described antioxidant is antioxidant 1010, antioxidant 1076, oxidation inhibitor 1024, oxidation inhibitor 168,3,3 '-propane thioic acid bay alcohol ester (DLTP), 3,3 '-the stearic alcohol ester (DSTP), 4,4 of propane thioic acid '-the choosing any one kind of them or several mixtures of thiobis (6-tertiary butyl-3-cresols).
And described superfine powder is choosing any one kind of them or several mixtures in lime carbonate, potter's clay class, talcum powder, silicon-dioxide, wollastonite or the white carbon black of particle diameter between 2500 orders～12500 orders.
And described coupling agent is selected from choosing any one kind of them or several mixtures in three oleoyl isopropyl titanates, two (dioctylphosphato) isopropyl titanate, diisostearoyl ethylene titanate, two (dioctylphosphato) metatitanic acid second diester, four hot oxygen titaniums two [two (tridecyl) phosphorous acid ester], four hot oxygen titaniums two (two lauric acid phosphorous acid esters), the DL-411 type aluminate coupling agent.
Beneficial effect of the present invention and advantage are:
1. reasonably to add particle diameter be 2500 orders～12500 purpose superfine powders to this silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound internal medicine, the superfine powder that makes interpolation by modification by inorganic nature to organic sex reversal, change into the oleophilic drainage performance by surface hydrophilic oleophobic performance, the problem of particle aggregation and bad dispersibility when successfully having solved the superfine powder interpolation, it is dispersed and compatible to make the silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound improve, improvement system flowing property and processing characteristics, and can give twisted polyethylene cable goods better physical mechanical property, improved toughness and erosion-resisting characteristics.
2. the superfine powder used of the present invention, its particle diameter of 90% 1～5 μ m had both had and had strengthened toughness reinforcing advantage, did not have the shortcoming of " easily reunite, the difficult dispersion " of similar nano-powder again.
3. the present invention can be according to practical situation, under the prerequisite that does not reduce performance index, select for use the superfine powder of different additions to reach the purpose that reduces production costs, can save 5%～15% cost according to different additions and the product comparison of not adding superfine powder, improve competition capability effectively.
Embodiment
The present invention is described in further detail by following examples, and following embodiment is illustrative, is not determinate, can not limit protection scope of the present invention with following embodiment.
Embodiment 1:
100 parts of water-ground limestones (6000 order) are put into the high mixer high speed mix, temperature begins dehumidifier when reaching 90 ℃, after temperature reaches 105 ℃, adds 1.25 parts of coupling agents;
Mix to stir 10min, the compound in the high mixer is put in the cold mixer cooled off then, be cooled to the water-ground limestone (6000 order) that discharging after 30 ℃ obtains modification;
With 100 parts of ldpe resins (MFR=2.3g/10min, density 0.92g/cm
3), the water-ground limestone (6000 order) of 160 parts of modifications, 4 parts of dibutyl tin laurates, 6 parts of antioxidant 1010s, put into cold mixer, mix and stir 5min, the material of emitting extruding pelletization on twin screw extruder, extrude back pelletizing, cooling, drying, the catalysis masterbatch of silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound.
The catalysis masterbatch of ldpe resin and silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound is dry in Vacuumdrier according to 95/5 ratio, 80 ℃ of drying temperatures, time of drying 10min, catalysis masterbatch with dried silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound, ldpe resin is put into cold mixer, add 2 parts of vinyltriethoxysilanes and 0.2 part of dicumyl peroxide, mix to stir behind the 5min discharging silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound finished product, carry out cable and extrude processing, this finished cable soaks after 8 hours in 80 ℃ of hot water, test data is as follows: tensile strength 18.5MPa, profound rate 430% ruptures, gel content 65%, heat is extended maximum elongation rate 20% under the load, volume specific resistance 1.1 * 10
14
Embodiment 2:
100 parts of potter's clay (3000 order) are put into the high mixer high speed mix, temperature begins dehumidifier when reaching 90 ℃, after temperature reaches 105 ℃, adds 1 part of coupling agent
Mix to stir 10min, the compound in the high mixer is put in the cold mixer cooled off then, be cooled to the potter's clay that discharging after 30 ℃ obtains modification;
With 100 parts of ldpe resins (MFR=2.0g/10min, density 0.915g/cm
3), the potter's clay (3000 order) of 75 parts of modifications, 5 parts of dibutyl tin laurates, 1076,0.5 part of antioxidant 1024 of 1.5 parts of antioxidants puts into cold mixer, mix and stir 5min, the material of emitting extruding pelletization on twin screw extruder, extrude back pelletizing, cooling, drying, the catalysis masterbatch of silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound.
The catalysis masterbatch of ldpe resin and silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound is dry in Vacuumdrier according to 80/20 ratio, 80 ℃ of drying temperatures, time of drying 10min, catalysis masterbatch with dried silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound, ldpe resin is put into cold mixer, add 2 parts of vinyltrimethoxy silanes and 0.2 part of mistake benzoyl peroxide, mix to stir behind the 5min discharging silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound finished product, carry out cable and extrude processing, this finished cable soaks after 8 hours in 80 ℃ of hot water, test data is as follows: tensile strength 24.8MPa, profound rate 390% ruptures, gel content 63%, heat is extended maximum elongation rate 25% under the load, volume specific resistance 1.4 * 10
14
Claims (7)
1. silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound and technology of preparing thereof, it is characterized in that: its component and parts by weight are respectively:
80～110 parts of ldpe resins;
0.5～5 part in silane;
0.1～10 part of peroxide initiator;
0.1～10 part of silanol condensation catalyst;
0.1～10 part of antioxidant;
1～30 part of ultra-fine rigid particles;
0.05～5 part of coupling agent.
Its technology of preparing may further comprise the steps:
(1) superfine powder of preparation modification:
Superfine powder is put into the high mixer high speed to mix, temperature begins dehumidifier when reaching 80 ℃～90 ℃, after temperature reaches 105 ℃～150 ℃, add coupling agent and mix stirring 5～10min, then the compound in the high mixer is put in the cold mixer and cooled off, be cooled to the superfine powder that discharging after 30 ℃～50 ℃ obtains modification;
(2) the catalysis masterbatch of preparation silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound:
With ldpe resin, superfine powder, catalyzer, antioxidant is put into cold mixer, emit material and extruding pelletization on twin screw extruder after mixing stirring 2～10min, one district's temperature is 120～150 ℃ from the spout to the die head, 140～170 ℃ of two district's temperature, 150～180 ℃ of three district's temperature, 150～180 ℃ of four district's temperature, 150～180 ℃ of five district's temperature, 160～190 ℃ of six district's temperature, 160～190 ℃ of seven district's temperature, 170～200 ℃ of eight district's temperature, 170～200 ℃ of nine district's temperature, residence time are 0.5～2min, and engine speed is 200～600r/min, discharging, extrude the back pelletizing, cooling, drying, the catalysis masterbatch of silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound.
(3) preparation silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound:
Catalysis masterbatch, the low-density polyethylene resin of silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound is dry in Vacuumdrier, 70～90 ℃ of drying temperatures, time of drying 5～20min, catalysis masterbatch, the ldpe resin of dried silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound are put into cold mixer, add linking agent and initiator, mix stir behind 2～10min discharging silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound finished product.
2. silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound according to claim 1 and technology of preparing thereof, it is characterized in that: described ldpe resin melt flow rate (MFR) is (190 ℃ of 0.5～3.0g/10min, 2.16kg record under the condition), density is 0.915～0.928g/cm
3
3. silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound according to claim 1 and technology of preparing thereof is characterized in that: described silane general formula is RSi (OR ')
3Wherein R is undersaturated olefin group, R ' is generally methyl or ethyl, can be choosing any one kind of them or several mixtures in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (2-methoxyethoxy) silane or the methacryloxypropyl triethoxyl silane.
4. silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound according to claim 1 and technology of preparing thereof, it is characterized in that: described initiator is a peroxide initiator, be selected from dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5 di-tert-butyl peroxides or benzoyl peroxide, the described decomposition of initiator transformation period is below 5 minutes.5. silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound according to claim 1 and technology of preparing thereof is characterized in that: described silanol condensation catalyst is selected from one or more in dibutyl tin laurate, two sad dibutyl tins, the dibutyltin diacetate.
6. silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound according to claim 1 and technology of preparing thereof, it is characterized in that: described antioxidant is antioxidant 1010, antioxidant 1076, oxidation inhibitor 1024, oxidation inhibitor 168,3,3 '-propane thioic acid bay alcohol ester (DLTP), 3, the choosing any one kind of them or several mixtures of the stearic alcohol ester (DSTP) of 3 '-propane thioic acid, 4,4 '-thiobis (6-tertiary butyl-3-cresols).
7. silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound according to claim 1 and technology of preparing thereof is characterized in that: described superfine powder is choosing any one kind of them or several mixtures in lime carbonate, potter's clay class, talcum powder, silicon-dioxide, wollastonite or the white carbon black of particle diameter between 2500 orders～12500 orders.
8. silane cross-linked polyethylene cable with ultrafine rigid particles PP Pipe Compound according to claim 1 and technology of preparing thereof is characterized in that: described coupling agent is selected from choosing any one kind of them or several mixtures in three oleoyl isopropyl titanates, isopropyl tri (dioctylphosphato)titanate, diisostearoyl ethylene titanate, two (dioctylphosphato) metatitanic acid second diester, four hot oxygen titaniums two [two (tridecyl) phosphorous acid ester], four hot oxygen titaniums two (two lauric acid phosphorous acid esters), the DL-411 type aluminate coupling agent.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2007101508641A CN101456986A (en) | 2007-12-11 | 2007-12-11 | Special material for silane cross-linked polyethylene cable with ultrafine rigid particles and preparation technology thereof |
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| CNA2007101508641A CN101456986A (en) | 2007-12-11 | 2007-12-11 | Special material for silane cross-linked polyethylene cable with ultrafine rigid particles and preparation technology thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009193A (en) * | 2016-07-08 | 2016-10-12 | 浙江太湖远大新材料股份有限公司 | Silane crosslinked polyethylene insulating material for silver gray wires and cables and preparation method of insulating material |
| CN106084423A (en) * | 2016-08-02 | 2016-11-09 | 合肥文武信息技术有限公司 | A kind of polyethylene communications cable material with absorption affinity |
| CN106220988A (en) * | 2016-08-23 | 2016-12-14 | 江苏鑫丰塑业有限公司 | A kind of improvement warm water crosslinking black insulated aerial cable material |
| CN106397897A (en) * | 2016-08-31 | 2017-02-15 | 余姚市楷瑞电子有限公司 | Crosslinkable composition and crosslinked cable coating material |
| CN110732348A (en) * | 2019-08-09 | 2020-01-31 | 浙江爱康实业有限公司 | silane crosslinked polyethylene composite high-efficiency catalyst and silane crosslinked polyethylene containing same |
| CN117801406A (en) * | 2023-12-28 | 2024-04-02 | 苏州亨利通信材料有限公司 | Silane crosslinked polyethylene cable insulating material and preparation method thereof |
-
2007
- 2007-12-11 CN CNA2007101508641A patent/CN101456986A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009193A (en) * | 2016-07-08 | 2016-10-12 | 浙江太湖远大新材料股份有限公司 | Silane crosslinked polyethylene insulating material for silver gray wires and cables and preparation method of insulating material |
| CN106084423A (en) * | 2016-08-02 | 2016-11-09 | 合肥文武信息技术有限公司 | A kind of polyethylene communications cable material with absorption affinity |
| CN106220988A (en) * | 2016-08-23 | 2016-12-14 | 江苏鑫丰塑业有限公司 | A kind of improvement warm water crosslinking black insulated aerial cable material |
| CN106397897A (en) * | 2016-08-31 | 2017-02-15 | 余姚市楷瑞电子有限公司 | Crosslinkable composition and crosslinked cable coating material |
| CN110732348A (en) * | 2019-08-09 | 2020-01-31 | 浙江爱康实业有限公司 | silane crosslinked polyethylene composite high-efficiency catalyst and silane crosslinked polyethylene containing same |
| CN117801406A (en) * | 2023-12-28 | 2024-04-02 | 苏州亨利通信材料有限公司 | Silane crosslinked polyethylene cable insulating material and preparation method thereof |
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Open date: 20090617 |