CN100370556C - Unsaturated carboxylic acid salt modified WTR insulation material and preparing method - Google Patents
Unsaturated carboxylic acid salt modified WTR insulation material and preparing method Download PDFInfo
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- CN100370556C CN100370556C CNB2005101110211A CN200510111021A CN100370556C CN 100370556 C CN100370556 C CN 100370556C CN B2005101110211 A CNB2005101110211 A CN B2005101110211A CN 200510111021 A CN200510111021 A CN 200510111021A CN 100370556 C CN100370556 C CN 100370556C
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Abstract
The present invention provides a modified water-tree retardant insulation material of unsaturated carboxylate, and a preparation method thereof. The modified water-tree retardant insulation material is made from unsaturated carboxylic acid, alkali, or metal oxide, polyolefine resin, initiators or crosslinking agents and plastic processing agents, and is prepared with a melt blending method. The modified water-tree retardant insulation material prepared by the method of the present invention can reduce water-tree-shaped tissue generated by hydropower aging. Therefore, the insulation material of the present invention is used for cable insulation layers.
Description
Technical field:
The present invention relates to a kind of insulating material and preparation method, it is a kind of water-tree retardant insulating materials and preparation method of salt unsaturated carboxylic acid modification.
Background technology:
Plastic power cable is owing to lay easily, and cheap, easy to process, dielectric property and good mechanical property are widely used in power transmission and distribution project.Yet this power cable that insulate with the extrusion molding dielectric be installed in water or contact with water most probably underground the time, because when organic polymer material is in the electric field under the situation that has liquid state or vapourous water to exist for a long time, the water tree network can occur, cause the lost of life.Therefore, particularly medium and high voltage cable may produce dielectric breakdown because of the phenomenon that is called " water tree " in this area, causes cable destroyed.
Anti-in order to increase organic insulating material owing to water is set the ability of degrading, the method that many minimizings and anti-sealing tree forms and increases has been proposed.Such as can be, find the general argumentation of this phenomenon in 671 (Turbett et al.), U.S. Patent number 4,206,260 (Mc Mahon) and the U.S. Patent number 4,499,013 (Barlow et al.) from U.S. Patent number 4,440.
U.S. Patent number 4,440,671 disclose a kind of tree resistant compositions that can be used as cable insulation, and said composition comprises a kind of aniline of hydrocarbon replacement and the polyethylene glycol of HMW.Yet polyethylene glycol is that as the shortcoming of anti-water tree additive it is hydrophilic, and is poor with nonpolar polyolefin compatibility.Because its difficult compatibility, for being to be diffused on the whole polyolefin isolator by droplet, and these drops are as the sucking-off point that spreads water in the insulator by the people for polyethylene glycol.Along with water accumulate in additive around, will produce the zone that local height is assembled water, and should may oneself cause occurring defective in the zone.Therefore, tree forms although the polyethylene glycol additive can postpone water, and at life period, through after the certain time interval, it often causes the integral body of water tree amount in the insulator to increase.
As U.S. Patent number, 305,849, Chinese patent CN1175065A and Chinese patent CN 1050728A are pointed, with hydrophilic material such as the polyethylene glycol and the ethylene-vinyl acetate copolymer etc. of compatible polyolefin difference some shortcoming is arranged all, poor such as compatibility, volatility etc. can not the good water-tree retardant insulating materials of processability.
Summary of the invention:
The objective of the invention is to have the component of enough hydrophilies and the fine diffusion of energy, prepare a kind of insulating material with water tree resistant property by interpolation in vistanex.
The water-tree retardant insulating materials of salt unsaturated carboxylic acid modification of the present invention composed as follows:
0.1-10 the plastic processing additives of the initator of the vistanex of the alkali of the unsaturated carboxylic acid of weight portion, 0.1-10 weight portion or metal oxide, 90-99 weight portion, 0.01-5 weight portion or crosslinking agent and 1-10 weight portion.
The unsaturated carboxylic acid that the present invention adopts is selected from acrylic acid, methacrylic acid or maleic anhydride.
Alkali or its oxide that alkali that the present invention adopts or metal oxide are selected from sodium, potassium, lithium, magnesium, calcium, iron, zinc, cobalt, nickel or copper.
The vistanex that the present invention adopts is selected from low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), LLDPE, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate ethyl ester copolymer, ethylene-propylene copolymer, ethylene-propylene-diene terpolymers or polypropylene or its mixture.
Initator or crosslinking agent that the present invention adopts are selected from dicumyl peroxide, laurylperoxide acyl, azodiisobutyronitrile, di-t-butyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexin or 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexane tert-butyl group hydrogen.
The plastic processing additives that the present invention adopts has antioxidant, ultraviolet absorber, antistatic agent, filler, slipping agent, stabilizer, crosslinked kicker, viscosity-control additive, colouring agent, plasticizer.
The preparation method of the water-tree retardant insulating materials of salt unsaturated carboxylic acid modification of the present invention is as follows:
It is mixing earlier the plastic processing additives of the vistanex of the alkali of 0.1-10 weight portion or metal oxide, 90-99 weight portion and 1-10 weight portion to be put into banbury, treat to add after the polyolefin fusion unsaturated carboxylic acid of 0.1-10 weight portion, last initator or the crosslinking agent that adds the 0.01-5 weight portion again, melting temperature is 100-200 ℃, whole mixing time is 5-30 minute, obtains a kind of insulating composition for preventing water-tree shape material of salt unsaturated carboxylic acid modification.
The water-tree retardant insulating materials of the salt unsaturated carboxylic acid modification that the present invention obtains, a kind of unsaturated carboxylic acid and alkali or metal oxide have been adopted, original position generates salt unsaturated carboxylic acid in melting mixing, and this salt unsaturated carboxylic acid polymerization reaction take place (comprising glycerol polymerization and homopolymerization) under the initiation of initator or crosslinking agent generates polymer.The insulating material of this in-situ polymerization salt unsaturated carboxylic acid modification has anti-water tree characteristic, wherein salt unsaturated carboxylic acid has enough hydrophilies, and in material, spread with the anti-sealing of hydrone bonding, this salt unsaturated carboxylic acid is partially grafted in the strand of vistanex simultaneously, improved the compatibility of salt unsaturated carboxylic acid homopolymers and vistanex, prevented the loss and the gathering of salt unsaturated carboxylic acid and kept totally distributing equably diffusion; Compare with traditional cable insulation material and not only to have good mechanical performance and dielectric property, and can suppress or avoid the generation of water tree phenomenon effectively, be specially adapted to the insulating barrier of medium and high voltage cable.
Embodiment:
The present invention will be described in more details technical scheme of the present invention by following concrete embodiment, but the present invention is not limited to embodiment proposed below.
The mechanical property evaluation method of the water-tree retardant insulating materials of salt unsaturated carboxylic acid modification of the present invention adopts the IEC60811 standard; The water tree resistant property evaluation reference adopts the ASTM6097-01a standard; Banbury among the embodiment adopts the Haake torque rheometer.
Embodiment 1:
Earlier with 0.32 gram NaOH, that 150 gram LLDPEs are put into the Haake torque rheometer is mixing, in the 0.57 gram acrylic acid of adding after the polyethylene fusion, add 0.1 gram dicumyl peroxide at last again, melting temperature is 170 ℃, whole mixing time is 20 minutes, obtains the water-tree retardant insulating materials of salt unsaturated carboxylic acid modification.
Embodiment 2:
Earlier with 0.32 gram NaOH, that 150 gram LLDPEs are put into the Haake torque rheometer is mixing, in the 0.57 gram acrylic acid of adding after the polyethylene fusion, add 3.0 gram dicumyl peroxides at last again, melting temperature is 130 ℃, whole mixing time is 10 minutes, obtains the water-tree retardant insulating materials of salt unsaturated carboxylic acid modification.
Table one performance relatively
Commercially available cable insulating material is the LL4004 of U.S. EXXON company.
From last table one, can significantly find out, the water tree length of the water-tree retardant insulating materials of above-mentioned two the resulting salt unsaturated carboxylic acid modifications of embodiment of the present invention reduces 35%-60% than the water tree length of commercially available cable insulating material, hot strength and elongation at break and commercially available cable insulating material are approaching simultaneously, this shows that the water-tree retardant insulating materials of the salt unsaturated carboxylic acid modification that the present invention obtains has good anti-water tree characteristic, can also keep mechanical property preferably simultaneously.
Claims (2)
1. the water-tree retardant insulating materials of salt unsaturated carboxylic acid modification is characterized in that composed as follows: the plastic processing additives of the vistanex of the alkali of the unsaturated carboxylic acid of 0.1-10 weight portion, 0.1-10 weight portion or metal oxide, 90-99 weight portion, the initator of 0.01-5 weight portion or crosslinking agent and 1-10 weight portion; Wherein unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid or maleic anhydride; Alkali or metal oxide are selected from alkali or its oxide of sodium, potassium, lithium, magnesium, calcium, iron, zinc, cobalt, nickel or copper; Vistanex is selected from low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), LLDPE, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate ethyl ester copolymer, ethylene-propylene copolymer, ethylene-propylene-diene terpolymers or polypropylene or its mixture; Initator or crosslinking agent are selected from dicumyl peroxide, laurylperoxide acyl, azodiisobutyronitrile, di-t-butyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexin or 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexane tert-butyl group hydrogen; Plastic processing additives has antioxidant, ultraviolet absorber, antistatic agent, filler, slipping agent, stabilizer, crosslinked kicker, viscosity-control additive, colouring agent, plasticizer.
2. the preparation method of the water-tree retardant insulating materials of salt unsaturated carboxylic acid modification as claimed in claim 1 is characterized in that the preparation method is as follows:
It is mixing earlier the plastic processing additives of the vistanex of the alkali of 0.1-10 weight portion or metal oxide, 90-99 weight portion and 1-10 weight portion to be put into banbury, treat to add after the polyolefin fusion unsaturated carboxylic acid of 0.1-10 weight portion, last initator or the crosslinking agent that adds the 0.01-5 weight portion again, melting temperature is 100-200 ℃, whole mixing time is 5-30 minute, obtains a kind of insulating composition for preventing water-tree shape material of salt unsaturated carboxylic acid modification;
Wherein unsaturated carboxylic acid is selected from acrylic acid, methacrylic acid or maleic anhydride; Alkali or metal oxide are selected from alkali or its oxide of sodium, potassium, lithium, magnesium, calcium, iron, zinc, cobalt, nickel or copper; Vistanex is selected from low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), LLDPE, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-methyl methacrylate ethyl ester copolymer, ethylene-propylene copolymer, ethylene-propylene-diene terpolymers or polypropylene or its mixture; Initator or crosslinking agent are selected from dicumyl peroxide, laurylperoxide acyl, azodiisobutyronitrile, di-t-butyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexin or 2,5-dimethyl-2,5-two (t-butyl peroxy)-hexane tert-butyl group hydrogen; Plastic processing additives has antioxidant, ultraviolet absorber, antistatic agent, filler, slipping agent, stabilizer, crosslinked kicker, viscosity-control additive, colouring agent, plasticizer.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101110211A CN100370556C (en) | 2005-12-01 | 2005-12-01 | Unsaturated carboxylic acid salt modified WTR insulation material and preparing method |
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| CNB2005101110211A CN100370556C (en) | 2005-12-01 | 2005-12-01 | Unsaturated carboxylic acid salt modified WTR insulation material and preparing method |
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| CN1801401A CN1801401A (en) | 2006-07-12 |
| CN100370556C true CN100370556C (en) | 2008-02-20 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5056601B2 (en) * | 2008-06-10 | 2012-10-24 | 日立電線株式会社 | Non-halogen flame retardant thermoplastic elastomer resin composition, method for producing the same, and electric wire / cable using the same |
| EP2901459B1 (en) | 2012-09-27 | 2017-04-19 | Dow Global Technologies LLC | Process for reducing peroxide migration in crosslinkable ethylene-based polymer compositions |
| WO2015013138A1 (en) * | 2013-07-23 | 2015-01-29 | Fina Technology, Inc. | Metallic acrylate salts to increase polymer melt streingth |
| CN107043528B (en) * | 2016-12-27 | 2019-03-08 | 天津金发新材料有限公司 | A kind of enhancing PC composition |
| CN114163932A (en) * | 2020-09-11 | 2022-03-11 | 上海共城通信科技有限公司 | Preparation method of ionic resin packaging adhesive film |
| 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 |
| CN1318200A (en) * | 1998-09-17 | 2001-10-17 | 泰科电子英国有限公司 | Electrical wire insulation material |
| JP2004349183A (en) * | 2003-05-23 | 2004-12-09 | Asahi Denka Kogyo Kk | Vinyl chloride-based resin composition for transparent electric wire |
-
2005
- 2005-12-01 CN CNB2005101110211A patent/CN100370556C/en not_active Expired - Fee Related
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 |
| CN1318200A (en) * | 1998-09-17 | 2001-10-17 | 泰科电子英国有限公司 | Electrical wire insulation material |
| JP2004349183A (en) * | 2003-05-23 | 2004-12-09 | Asahi Denka Kogyo Kk | Vinyl chloride-based resin composition for transparent electric wire |
Non-Patent Citations (1)
| Title |
|---|
| 接枝甲基丙烯酸对氢氧化铝阻燃聚乙烯电缆料电气性能的改善. 苏战排，韦平，汪根林，江平开，周围.电线电缆，第6期. 2003 * |
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Assignee: Zhengzhou Huali Cable Co., Ltd. Assignor: Hangzhou Tongda macromolecule material Co., Ltd. Contract record no.: 2011410000100 Denomination of invention: Unsaturated carboxylic acid salt modified WTR insulation material and preparing method Granted publication date: 20080220 License type: Exclusive License Open date: 20060712 Record date: 20110802 |
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