CN101104713B - Water tree resistant polyolefin electrical insulation composition - Google Patents
Water tree resistant polyolefin electrical insulation composition Download PDFInfo
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- CN101104713B CN101104713B CN2006100288315A CN200610028831A CN101104713B CN 101104713 B CN101104713 B CN 101104713B CN 2006100288315 A CN2006100288315 A CN 2006100288315A CN 200610028831 A CN200610028831 A CN 200610028831A CN 101104713 B CN101104713 B CN 101104713B
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Abstract
The invention discloses a water-tree retardant polyolefin electrical insulation composition which contains 0.2 to 0.6 phr sugar alcohol polymer used as water-tree retardant growth promoter. What is better is that the sugar alcohol polymer contains no more than 8 phr vinyl copolymer. The sugar alcohol polymer can improve the water-tree retardant performance of the insulation material. Moreover, the sugar alcohol polymer and the vinyl copolymer have synergistic effect to inhibit the water-tree growing, and have good dispersity and will not influence the manufacture of the insulation material. The polyolefin electrical insulation composition can be used in medium voltage power cable and prolong the service life of the power cable.
Description
Technical field
The present invention relates to the electrically insulating material field, the polyolefin electrical insulation composition of particularly a kind of anti-water tree.
Background technology
Electric member, generally including with the polyolefine as the insulation material layer in the power cable is the electrical insulation composition of main component, presses almost one of percentage hundred conventional crosslinked polyethylene of employing (XLPE) insulation of power cable of grade among for example domestic present 6～35kV.In the last few years, the rate of breakdown of the crosslinked polyetylene insulated medium-pressure power cable of domestic routine rose obviously, and the cable body cause faults is an insulation composition growth water tree and cause early stage damage.Especially be installed in the cable in the southern wet environment, water tree is taken place very general, indivedual serious branch length near insulation thickness 70%! Increasing cable user and cables manufacturing factory have realized that and must take measures to avoid early and contain the trend that the water tree causes cable bad to rise.
So-called " water tree " is meant the existence of insulating material because of micropore and impurity, and from inside and outside moisture, brings out the microchannel or the tree-shaped pipeline of radially development in the part of insulation defect, thereby cause decreasing insulating.The water tree is the storage area of water, just may become obviously when electric field is added on the electric insulation.For avoiding or reduce the generation of water tree, usually in electrical insulation composition, add anti-water tree growth promoter, as add ethylenic copolymer (Dang Zhimin etc. the water tree increment study of ethylene-acrylic acid copolymer modified poly ethylene. Proceedings of the CSEE .2001 (9): 18-21.) etc.
Summary of the invention
The purpose of this invention is to provide the polyolefin electrical insulation composition that a kind of new anti-water is set, it has added anti-water tree growth promoter unlike the prior art.
The present invention realizes above-mentioned purpose by following technical proposal.The polyolefin electrical insulation composition of anti-water tree of the present invention, it comprises that 0.2～0.6phr (every hectogram umber) glycitols polymkeric substance is as anti-water tree growth promoter.
The said glycitols polymkeric substance of the present invention is meant that the aldehyde radical of sugar is reduced into the compound that obtains behind the alcohol radical, it typically is the high molecular polymer of natural origin, as Sorbitol Powder, Xylitol, N.F,USP MANNITOL and tetrahydroxybutane etc.The glycitols polymkeric substance adds in the polyolefine as nucleator, to improve the regularity of pure polyolefin compound nucleus, has reduced the influence of space charge to insulating material, thereby has improved its water tree resistant property; Its consumption all can influence water tree resistant property too much very little, the preferred 0.4phr of the present invention.
More preferably, this anti-water tree growth promoter also comprises and is no more than 8phr, is preferably the ethylenic copolymer of 3～6phr.
Said ethylenic copolymer can be any ethylenic copolymer of setting growth promoter in the prior art as anti-water, preferably from ethylene-vinyl acetate copolymer (EVA), and ethene and acrylate copolymers such as methyl acrylate or butyl acrylate.The present invention utilizes the wetting ability of the polar group-carbonyl that contains in the ethylenic copolymer molecular structure, and water molecules further is condensed into water droplet in the prevention material.
This ethylenic copolymer and glycitols polymkeric substance share has synergy, and its best proportioning is 15:1 (w/w).
The main component of polyolefin electrical insulation composition of the present invention is preferably polyethylene kind, as polyethylene low, middle density, is cross-linking type.
The present invention more preferably is used for the crosslinked polyetylene insulated composition of medium-pressure power cable, and it contains the matrix polyvinyl resin of 100phr, the linking agent of 2～3phr and the oxidation inhibitor of 0.2～0.4phr usually.
Wherein, this polyvinyl resin is new LDPE (film grade) (LDPE), and its melt temperature is lower, between 100 ℃～135 ℃, and processing easily; Described linking agent is meant the cross-linking type insulating material used additives that can change linear macromolecule into stereoscopic (tridimensional network) macromolecular structure, comprise peroxyde crosslinked dose that from organo-peroxide, selects, for example dicumyl peroxide (DCP), connection (tert-butyl hydroperoxide-sec.-propyl) benzene, tert butyl isopropyl benzene peroxide and composition thereof etc., the preferred DCP of the present invention; And described oxidation inhibitor is general insulating material usual auxiliaries, can improve the ageing-resistant performance of material, four [β-(3 ' for example, 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), Tyox B (DLTP), 4,4 '-thiobis (3 methy 6 tert butyl phenol) (antioxidant 300 #), 2,2 '-thiobis (4-methyl-6-tert butyl phenol) (oxidation inhibitor 1081) and composition thereof etc.
The polyolefin electrical insulation composition of the anti-water tree of the present invention; can according to existing conventional extruding and pelletizing process (as document Hu Zhenglong. twin screw plastic milling extruding pelletization unit. lathe and hydraulic pressure; 2003.3 middle disclosed method) produce; for domestic Insulation Material factory; existing, particularly medium voltage electricity need not to transform and can produce with crosslinked polyetylene insulated composition production line, the existing installation of state inner cable factory also can use this invention fully.To adopt and the general medium-pressure power cable identical extruding and pelletizing process of insulating material, can satisfy YJ-35 requirement among the JB/T 10437-2004.
The present invention adds anti-water tree growth promoter in polyolefin electrical insulation composition, the particularly cross-linked polyethylene insulating material to by physical means, improved the water tree resistant property of cross-linked polyethylene insulating material, delay the growth time of cross-linked polyethylene insulating material water tree in the high-frequency water surrounding of high field intensity, perhaps suppressed the growth of water tree.
Description of drawings
Fig. 1 is that homemade common 35kV XLPE insulation composition causes water tree test photo.
Fig. 2 causes water tree test photo for XLPE insulation composition of the present invention.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Embodiment 1～6 and comparative example's 1～4 prescription such as following table:
Matrix LDPE resin among the various embodiments described above and the comparative example is extruded by Switzerland BUSSKG1418 twin screw extruder group, in extrusion, add anti-water tree growth promoter, oxidation inhibitor and linking agent, can obtain anti-water tree XLPE insulation composition in the pelletizing of die head place.
Wherein, matrix LDPE resin is Kingsoft, Shanghai petroleum chemicals; Crosslink agent DCP (dicumyl peroxide) is a Nanjing Holley bright science, industry and trade company limited product; Antioxidant 1010 is a Shanghai Zhuo Jia chemical industry company limited product, and 300# is Milan, Nanjing chemical industry company limited product, and 1081 is Switzerland Ciba company product, and DLTP is a Switzerland Ciba company product; Ethylenic copolymer EVA, EBA (ethylene-propylene acid butyl ester) are for raising sub-BASF product (model is respectively W3510k and 3427AC), and EMA (ethylene-methyl acrylate) is E.I.Du Pont Company's product; The glycitols polymkeric substance has a responsibility for limitting company's product for Japan east and company, Korea S Bao Le company, Henan, Tangyin, Anyang are prosperous.
Under equal test conditions, the foregoing description and comparative example are caused the test of water tree, with reference to ASTM D6097a " standard test methods of the relative tolerance of solid insulating material emitting shape water tree growth ", the anti-water tree characteristic of insulating material is represented by water tree growth resistant RWTG (Resistance To Water-Tree Growth):
In the formula: L is the distance of needle plate electrode; WTL is the maximum length of water tree.The result is as shown in the table, and the RWTG of homemade common middle pressure XLPE insulation composition (YJ-35KV of Shanghai Chemical Plant cross-linked polyethylene insulating material) is 6.3.
| Embodiment | WTL(mm) | L(mm) | RWTG |
| 1 | 0.31 | 3.2 | 10.3 |
| 2 | 0.19 | 3.2 | 16.8 |
| 3 | 0.25 | 3.2 | 12.8 |
| 4 | 0.22 | 3.2 | 14.5 |
| 5 | 0.17 | 3.2 | 18.8 |
| 6 | 0.13 | 3.2 | 24.6 |
| The comparative example 1 | 0.25 | 3.2 | 12.8 |
| 2 | 0.22 | 3.2 | 14.5 |
| 3 | 0.20 | 3.2 | 16.0 |
| 4 | 0.27 | 3.2 | 11.9 |
Fig. 1, Fig. 2 have shown the test-results of homemade common 35kV and the growth of the anti-water tree of XLPE insulation composition of the present invention.As seen, the present invention is by adding glycitols polymkeric substance or glycitols polymkeric substance and ethylenic copolymer as anti-water tree growth promoter, the existing XLPE insulation composition that does not add anti-water tree growth promoter has the effect of obvious inhibition water tree growth, and wherein glycitols polymkeric substance and ethylenic copolymer share and have more synergy.
Anti-water tree XLPE insulation composition of the present invention is applied to medium-pressure power cable, as the medium-pressure power cable of a kind of texture improvement of relating among fire-retardant medium-pressure power cable of a kind of low smoke and zero halogen category-A that relates among the patent CN01110765.0 " 35KV XLPE insulating low-smoke halogen-free category-A flame-proof power cable " and the CN01236106.2 " sheath is coated with the power cable of plastics conductive layer ".Under the environment of concentrating and have water to exist in strength of electric field, the present invention can suppress the growth of water tree in the insulation layer, so can prolong cable life.
Claims (6)
1. the polyolefin electrical insulation composition of an anti-water tree, it contains 0.2～0.6phr glycitols polymkeric substance as anti-water tree growth promoter; This anti-water tree growth promoter also comprises the ethylenic copolymer of 3～8phr; Wherein, described glycitols polymkeric substance is selected from Sorbitol Powder, Xylitol, N.F,USP MANNITOL and tetrahydroxybutane; This ethylenic copolymer is selected from ethylene-vinyl acetate copolymer and ethylene-acrylate copolymer, and this ethylene-acrylate copolymer is meant ethylene-methyl acrylate copolymer or ethylene-butyl acrylate copolymer.
2. polyolefin electrical insulation composition as claimed in claim 1 is characterized in that containing in the described polyolefin electrical insulation composition this glycitols polymkeric substance of 0.4phr.
3. polyolefin electrical insulation composition as claimed in claim 1 is characterized in that the content of this ethylenic copolymer in polyolefin electrical insulation composition is 3～6phr.
4. polyolefin electrical insulation composition as claimed in claim 1, the weight ratio that it is characterized in that this ethylenic copolymer and glycitols polymkeric substance is 15: 1.
5. as each described polyolefin electrical insulation composition of claim 1～4, it is characterized in that this polyolefin electrical insulation composition is the crosslinked polyetylene insulated composition that is used for medium-pressure power cable, said composition comprises the matrix polyvinyl resin of 100phr, the linking agent of 2～3phr and the oxidation inhibitor of 0.2～0.4phr.
6. polyolefin electrical insulation composition as claimed in claim 5, it is characterized in that this polyvinyl resin is a new LDPE (film grade), linking agent is a dicumyl peroxide, oxidation inhibitor is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, Tyox B, 4,4 '-thiobis (3 methy 6 tert butyl phenol) and 2, one or more of 2 '-thiobis (4-methyl-6-tert butyl phenol).
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| CN2006100288315A CN101104713B (en) | 2006-07-12 | 2006-07-12 | Water tree resistant polyolefin electrical insulation composition |
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| CN2006100288315A CN101104713B (en) | 2006-07-12 | 2006-07-12 | Water tree resistant polyolefin electrical insulation composition |
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| CN101104713B true CN101104713B (en) | 2010-09-08 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103824642B (en) * | 2014-02-10 | 2016-04-06 | 国家电网公司 | There is the flexible power cable of resistance to humid-ageing exposure |
| CN104311963A (en) * | 2014-10-30 | 2015-01-28 | 安徽电信器材贸易工业有限责任公司 | Anti-water tree polyethylene insulating cable material and preparation method thereof |
| CN106349552B (en) * | 2016-08-26 | 2018-03-02 | 江苏德威新材料股份有限公司 | A kind of water resistant tree semi-conductive shielding material and preparation method thereof |
| CN109251392A (en) * | 2018-08-14 | 2019-01-22 | 重庆瑞普电气实业股份有限公司 | A kind of water-tree-resistantmedium medium voltage crosslinked cable |
| CN109438807B (en) * | 2018-10-29 | 2020-12-01 | 北京科技大学 | Insulating material and preparation method and application thereof |
| CN112029167A (en) * | 2019-06-03 | 2020-12-04 | 南京中超新材料股份有限公司 | Water tree resistant crosslinked polyethylene insulation material |
| CN116023727A (en) * | 2022-12-29 | 2023-04-28 | 浙江万马高分子材料集团有限公司 | Water tree resistant overhead material and preparation method and application thereof |
| CN117736516B (en) * | 2024-02-07 | 2024-05-03 | 哈尔滨理工大学 | Polypropylene-based insulating material resistant to water tree branch aging and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050728A (en) * | 1989-07-26 | 1991-04-17 | 联合碳化化学品及塑料有限公司 | Tree resistant compositions |
| CN1175065A (en) * | 1996-06-21 | 1998-03-04 | 皮雷利·卡维有限公司 | Insulating composition for preventing water-tree shape material forming |
| JP2003147134A (en) * | 2001-08-27 | 2003-05-21 | Fujikura Ltd | Semiconductor watertight composition |
| CN1730531A (en) * | 2005-08-07 | 2006-02-08 | 无锡市沪安电线电缆有限公司 | Improved crosslinked polyetylene insulated material and power cable for 6KV and above |
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2006
- 2006-07-12 CN CN2006100288315A patent/CN101104713B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050728A (en) * | 1989-07-26 | 1991-04-17 | 联合碳化化学品及塑料有限公司 | Tree resistant compositions |
| CN1175065A (en) * | 1996-06-21 | 1998-03-04 | 皮雷利·卡维有限公司 | Insulating composition for preventing water-tree shape material forming |
| JP2003147134A (en) * | 2001-08-27 | 2003-05-21 | Fujikura Ltd | Semiconductor watertight composition |
| CN1730531A (en) * | 2005-08-07 | 2006-02-08 | 无锡市沪安电线电缆有限公司 | Improved crosslinked polyetylene insulated material and power cable for 6KV and above |
Non-Patent Citations (1)
| Title |
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| 党智敏,亢婕,屠德民.改性聚乙烯高聚物抑制水树的研究.高分子材料科学与工程第18卷 第3期.2002,第18卷(第3期),第94页. * |
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