CN1345893A - Process for preparing halogen-free flame-retardant organosilane cross-linked poly-ethylene cable material - Google Patents
Process for preparing halogen-free flame-retardant organosilane cross-linked poly-ethylene cable material Download PDFInfo
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- CN1345893A CN1345893A CN 00112600 CN00112600A CN1345893A CN 1345893 A CN1345893 A CN 1345893A CN 00112600 CN00112600 CN 00112600 CN 00112600 A CN00112600 A CN 00112600A CN 1345893 A CN1345893 A CN 1345893A
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Abstract
The preparation method of halogenless fire-retardant organosilane crosslinked poly-ethylene cable material is characterized by that using (by weight portion) 100 portions of low density polyethylene, 5-30 portions of ethylene copolymer elastomer, 2-5 portions of silane whose general formula is RSi (OR')3 (in which R is unsaturated olefine group and R' is methyl or ethyl generally), 0.1-0.5 portion of peroxide initiator, 0.05-0.02 portion of silane hydrolysis cross-linking catalyst, 70-150 portions of fire-retardant Mg(OH)2 and 5-30 portions of fire-retardant synergist and mixing them at 160-180 deg.c and granulating so as to obtain the invented product. Said invented cable material possesses excellent fire-retardant property, high tensile strength and large extension rate at break, and its oxygen index is above 30.
Description
The present invention relates to the preparation method's of halogen-free flame-proof cable sheath material, particularly organosilane cross-linked poly-ethylene cable material preparation method.
The main drawback of making the electric wire and cable jacket material with new LDPE (film grade) (hereinafter to be referred as polyethylene) is heat resistance difference and burning easily, crosslinkedly can improve poly heat resistance greatly.The method of polyethylene crosslinking mainly contains chemical crosslink technique, radiation crosslinking method and silane cross-linking method at present." chemistry circular " (1996 the 1st phase the 18th page) report, chemically crosslinked be with organo-peroxide as linking agent because required temperature, pressure-controlling is comparatively harsh in the cross-linking process, brought technologic difficulty; Radiation crosslinking is to utilize cobalt-60 or high-energy electron accelerator to obtain high-energy radiation to carry out crosslinkedly, and its shortcoming is that equipment manufacturing cost height, safety precaution problem complexity and high-energy radiation are big to the material property damage; Crosslinked with silicane is to integrate less investment, adaptability is strong and technology is easy important cross-linking method, is widely used in producing power cable, umbilical cable, overhead line, and also growing in the application of aspects such as telecommunication cable, heat-shrinkable tube.The low-voltage crosslinked cable market of 150V-1.5kV is mainly captured by organosilane cross-linked poly-ethylene cable both at home and abroad at present.
Polyethylene is by after the crosslinked with silicane, though its resistance toheat improves a lot, but still is not fire-retardant." chemistry with bonding " (1997 the 2nd phase the 109th page) point out that the research of organosilane crosslinked polyethylene non-halogen flame-retardant cable all is in the starting stage both at home and abroad, also do not have industrialized product to come out at present.Japanese Patent JP 04,149,238[92,149,238] reported and a kind of preparation method of fire-retardant organosilane crosslinked polyethylene mainly adopted aluminium hydroxide as fire retardant.But because Al (OH)
3Decomposition temperature lower (about about 180 ℃ just begin decompose), few with poly machine-shaping temperature head, in the machine-shaping process, make easily to produce bubble in the plastics and influence its performance.
The objective of the invention is poly crosslinked with silicane and halogen-free flameproof are organically combined, a kind of preparation method of organosilane cross-linked poly-ethylene cable sheath material of halogen-free flameproof is provided.
The preparation method of halogen-free flame-retardant organosilane cross-linked poly-ethylene cable sheath material of the present invention is characterized in that: with new LDPE (film grade), the ethylene copolymer elastomerics of 5-30 part, 2-5 part general formula of 100 parts of weight is RSi (OR ')
3Silane (wherein R is undersaturated olefin group, and R ' is methyl or ethyl normally), 0.1-0.5 part peroxide initiator and 0.05-0.2 part silane hydrolyzate crosslinking catalyst, 70-150 part fire retardant Mg (OH)
2With 5-30 part red phosphorus and/or expanded graphite retardant synergist, in Banbury mixer or forcing machine, carry out in 160-180 ℃ of temperature mixing, granulation.
Carrying out cable when extruding, be extruded on the cable core after placing the special-purpose forcing machine of cable to plastify the pellet of above-mentioned halogen-free flame-retardant organosilane cross-linked poly-ethylene cable sheath material, it is crosslinked to carry out hot water again.
Ethylene-vinyl acetate copolymer of the present invention is a kind of polar polymkeric substance, and it can improve the consistency between halogen-free flame retardants and the polyethylene.Ethylene copolymer elastomerics used in the present invention can be ethylene-propylene copolymer elastomerics or ethylene-vinyl acetate copolymer elastomerics.
Described general formula is RSi (OR ')
3Silane, can from vinyltriethoxysilane, vinyltrimethoxy silane or methacryloxypropyl triethoxyl silane, choose.
Described silane hydrolyzate crosslinking catalyst can be chosen from dibutyltin dilaurate, dibutyl tin dicaprylate or dibutyl tin diacetate, preferably dibutyltin dilaurate.
Described peroxide initiator can be from dicumyl peroxide, di-tert-butyl peroxide or 2, and 5-dimethyl-2 is chosen in the 5-dibutyl peroxidation hexane, preferably dicumyl peroxide.
Because Mg (OH)
2Be stable below 340 ℃, its decomposition temperature is than Al (OH)
3Much higher, so the present invention adopts Mg (OH)
2As halogen-free flame retardants, can avoid prior art to adopt aluminium hydroxide in plastics, to produce the defective of bubble easily as fire retardant.
Usually the particle diameter of fire retardant is more little, and its dispersiveness in polyethylene is just good more, and is just more little to the influence of the mechanical property of material.
Owing to use Mg (OH) separately
2The flame retarding efficiency of fire retardant is lower, and the present invention adopts and adds 5-30 part expanded graphite and/or red phosphorus flame-retardant synergistic agent, can improve the flame retardant properties of material greatly.When using red phosphorus as retardant synergist, the most handy organic resin such as melamine-formaldehyde resin carry out micro encapsulation; When adopting expanded graphite, select for use foam expansion 50-200 doubly for good.
Compared with prior art, the preparation method of halogen-free flame-retardant organosilane cross-linked poly-ethylene cable sheath material of the present invention, raw material is easy to get, and can utilize the production unit of existing organosilane cross-linked poly-ethylene cable material, and production technique is easy; The CABLE MATERIALS flame retardant properties that is obtained is good, and oxygen index is more than 30; And have good mechanical property, tensile strength height, elongation at break are big.
With embodiment the inventive method is done further concrete detailed explanation below.
Embodiment 1:
With the density of 100 parts of weight is 0.92g/cm
3, melting index is the new LDPE (film grade) of 2.0g/10min, 15 parts of ethylene-vinyl acetate copolymer elastomericss (wherein vinyl acetate content is 19%), 4 parts of vinyltriethoxysilanes, 0.4 part dicumyl peroxide, 0.15 part dibutyltin dilaurate hydrolyst, 70 parts of median sizes are 2 microns Mg (OH)
2Fire retardant, 10 parts is 100 expanded graphite retardant synergist through the red phosphorus flame-retardant synergistic agent behind the melamine-formaldehyde resin micro encapsulation and 20 parts of foam expansion, in Banbury mixer, carried out mixing 20 minutes in 160 ℃ temperature, move on the double roller plastic-making device then, open refining 5 minutes at 120 ℃, with the plastic cement film-making or the granulation of opening after the refining.After crosslinked 10 hours, its oxygen index is 32.5 by GB GB2406-80 test to resulting non-halogen flame-retardant cable through 90 ± 1 ℃ hot water, and tensile strength and elongation at break are respectively 12.8MPa and 426% by the result of GB GB 2951.5.7-82 test.
Vinyltriethoxysilane used in the foregoing description substitutes with vinyltrimethoxy silane or methacryloxypropyl triethoxyl silane, can obtain similar products like.
Embodiment 2:
New LDPE (film grade) raw material that will be identical, 20 parts of ethylene-vinyl acetate copolymer elastomericss (its specification is identical with embodiment 1), 5 parts of vinyltriethoxysilanes, 0.5 part of dicumyl peroxide, 0.2 part of dibutyltin dilaurate hydrolyst, 100 parts Mg (OH) with embodiment 1
2Fire retardant (its specification is identical with embodiment 1) and 30 parts of foam expansion are 50 expanded graphite retardant synergist, in Banbury mixer mixing 5 minutes in 180 ℃ temperature, move to then on the double roller plastic-making device, open refining 5 minutes at 120 ℃, the plastic cement film-making or the granulation of opening after the refining.The hot water that resulting non-halogen flame-retardant cable process is 90+1 ℃ is after crosslinked 10 hours, and recording its oxygen index according to embodiment 1 used standard is 32, and tensile strength is 12.4MPa, and elongation at break is 342%.
Embodiment 3:
New LDPE (film grade) raw material that will be identical, 30 parts of ethylene-vinyl acetate copolymer elastomericss (its specification is identical with embodiment 1), 2 parts of vinyltriethoxysilanes, 0.2 part of dicumyl peroxide, 0.05 part of dibutyltin dilaurate hydrolyst, 120 parts Mg (OH) with embodiment 1
2Fire retardant (its specification is identical with embodiment 1), 10 parts of foam expansion are red phosphorus flame-retardant synergistic agent behind 200 expanded graphite retardant synergist and the 10 parts of melamine-formaldehyde resin micro encapsulations in Banbury mixer in 170 ℃ temperature mixing 10 minutes, move on the double roller plastic-making device then, open refining 5 minutes at 120 ℃, with the plastic cement film-making or the granulation of opening after the refining.After crosslinked 10 hours, record its oxygen index according to embodiment 1 used standard is 33.5 to resulting non-halogen flame-retardant cable through 90 ± 1 ℃ hot water, and tensile strength is 11.7MPa, and elongation at break is 290%.
Embodiment 4:
New LDPE (film grade) raw material that will be identical, 10 parts of ethylene-propylene copolymer elastomericss, 3 parts of vinyltriethoxysilanes, 0.3 part of dicumyl peroxide, 0.10 part of dibutyltin dilaurate hydrolyst, 150 parts Mg (OH) with embodiment 1
2Fire retardant (its specification is identical with embodiment 1) and the 5 parts red phosphorus flame-retardant synergistic agent after through the melamine-formaldehyde resin micro encapsulation, its complete processing is identical with embodiment 1.Recording its oxygen index according to embodiment 1 used standard is 31, and tensile strength and elongation at break are respectively 12.0MPa and 382%.
If raw material same as the previously described embodiments is added in the twin screw extruder, extrusion condition is: barrel zone temperature 160-180 ℃, 180 ℃ of die temperatures, after molten mixture is extruded from the mouth mould, through cooling, pelletizing, drying, again on the double roller plastic-making device in 120 ℃ open the refining 5 minutes after film-making, can obtain similar products like through 90 ± 1 ℃ hot water after crosslinked 10 hours.
Claims (5)
1, a kind of preparation method of halogen-free flame-retardant organosilane cross-linked poly-ethylene cable material is characterized in that: with new LDPE (film grade), the ethylene copolymer elastomerics of 5-30 part, 2-5 part general formula of 100 parts of weight is RSi (OR ')
3Silane (wherein R is undersaturated olefin group, and R ' is methyl or ethyl normally), 0.1-0.5 part peroxide initiator and 0.05-0.2 part silane hydrolyzate crosslinking catalyst, 70-150 part fire retardant Mg (OH)
2With 5-30 part red phosphorus and/or expanded graphite retardant synergist, add in Banbury mixer or the forcing machine, carry out 160-180 ℃ of temperature mixing, granulation.
2, the preparation method of halogen-free flame-retardant organosilane cross-linked CABLE MATERIALS according to claim 1 is characterized in that described ethylene copolymer elastomerics is ethylene-propylene copolymer elastomerics or ethylene-vinyl acetate copolymer elastomerics.
3, the preparation method of halogen-free flame-retardant organosilane cross-linked CABLE MATERIALS according to claim 1 is characterized in that described silane can be vinyltriethoxysilane, vinyltrimethoxy silane or methacryloxypropyl triethoxyl silane.
4, the preparation method of halogen-free flame-retardant organosilane cross-linked CABLE MATERIALS according to claim 1, it is characterized in that described peroxide initiator is selected from dicumyl peroxide, di-tert-butyl peroxide or 2,5-dimethyl-2,5-di-tert-butyl peroxidation hexane, preferred dicumyl peroxide.
5, the preparation method of halogen-free flame-retardant organosilane cross-linked CABLE MATERIALS according to claim 1, it is characterized in that described silane hydrolyzate crosslinking catalyst is dibutyltin dilaurate, dibutyl tin dicaprylate or dibutyl tin diacetate, preferred dibutyltin dilaurate.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880417A (en) * | 2010-06-29 | 2010-11-10 | 武汉新天地特种电缆有限公司 | Silane crosslinked halogen-free flame-retardant polyethylene cable material and preparation method thereof |
| CN101341553B (en) * | 2005-12-22 | 2011-10-12 | 普雷斯曼电缆及系统能源有限公司 | Electric cable comprising foaming polyolefin isolator and manufacturing method thereof |
| CN101284930B (en) * | 2007-04-12 | 2011-10-26 | 日立电线株式会社 | Method for preparing non-halogen fire retardant thermoplastic combinations |
| CN101688046B (en) * | 2007-07-12 | 2012-06-20 | 株式会社自动网络技术研究所 | Flame-retardant silane-crosslinked olefin resin composition, insulated wire, and method for production of flame-retardant silane-crosslinked olefin resin |
| CN102982886A (en) * | 2012-11-28 | 2013-03-20 | 安徽埃克森科技集团有限公司 | Irradiation-crosslinked flame-retardant power cable and manufacturing method thereof |
| CN101633754B (en) * | 2009-05-22 | 2013-03-20 | 上海凯波特种电缆料厂有限公司 | Oil resistant type silane natural cross-linking low smoke halogen-free flame retardant polyolefin cable material and preparation method thereof |
| CN104610632A (en) * | 2015-01-14 | 2015-05-13 | 湖北祥源新材科技有限公司 | Colored high-performance and anti-static radiation cross-linked polyethylene foam material and preparation method thereof |
| CN105579519A (en) * | 2013-09-27 | 2016-05-11 | 古河电气工业株式会社 | Heat-resistant silane cross-linked resin molded article and production method for same, heat-resistant silane cross-linking resin composition and production method for same, silane masterbatch, and heat-resistant product employing heat-resistant silane cross-linked resin molded article |
| CN107189176A (en) * | 2017-07-20 | 2017-09-22 | 合肥安力电力工程有限公司 | A kind of CABLE MATERIALS with fire protection flame retarding function and preparation method thereof |
| CN109593265A (en) * | 2018-12-14 | 2019-04-09 | 成都鑫成鹏高分子科技股份有限公司 | A kind of lower shrinkage silane CABLE MATERIALS and preparation method thereof |
| TWI681994B (en) * | 2017-06-29 | 2020-01-11 | 美商陶氏全球科技有限責任公司 | Polyolefin composition |
| CN115433400A (en) * | 2022-07-25 | 2022-12-06 | 广东金阳光电缆实业有限公司 | Process for producing halogen-free flame-retardant cable |
| US11667735B2 (en) | 2017-06-29 | 2023-06-06 | Dow Global Technologies Llc | Polyolefin composition |
-
2000
- 2000-09-30 CN CN 00112600 patent/CN1345893A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101341553B (en) * | 2005-12-22 | 2011-10-12 | 普雷斯曼电缆及系统能源有限公司 | Electric cable comprising foaming polyolefin isolator and manufacturing method thereof |
| US8723041B2 (en) | 2005-12-22 | 2014-05-13 | Prysmian Cavi E Sistemi Energia S.R.L. | Electric cable comprising a foamed polyolefine insulation and manufacturing process thereof |
| CN101284930B (en) * | 2007-04-12 | 2011-10-26 | 日立电线株式会社 | Method for preparing non-halogen fire retardant thermoplastic combinations |
| CN101688046B (en) * | 2007-07-12 | 2012-06-20 | 株式会社自动网络技术研究所 | Flame-retardant silane-crosslinked olefin resin composition, insulated wire, and method for production of flame-retardant silane-crosslinked olefin resin |
| CN101633754B (en) * | 2009-05-22 | 2013-03-20 | 上海凯波特种电缆料厂有限公司 | Oil resistant type silane natural cross-linking low smoke halogen-free flame retardant polyolefin cable material and preparation method thereof |
| CN101880417A (en) * | 2010-06-29 | 2010-11-10 | 武汉新天地特种电缆有限公司 | Silane crosslinked halogen-free flame-retardant polyethylene cable material and preparation method thereof |
| CN102982886A (en) * | 2012-11-28 | 2013-03-20 | 安徽埃克森科技集团有限公司 | Irradiation-crosslinked flame-retardant power cable and manufacturing method thereof |
| CN105579519A (en) * | 2013-09-27 | 2016-05-11 | 古河电气工业株式会社 | Heat-resistant silane cross-linked resin molded article and production method for same, heat-resistant silane cross-linking resin composition and production method for same, silane masterbatch, and heat-resistant product employing heat-resistant silane cross-linked resin molded article |
| CN105579519B (en) * | 2013-09-27 | 2017-11-21 | 古河电气工业株式会社 | Heat resistance crosslinked with silicane resin-formed body and its manufacture method, heat resistance crosslinked with silicane resin combination and its manufacture method, silane masterbatch and the heat resistance product for having used heat resistance crosslinked with silicane resin-formed body |
| US10083776B2 (en) | 2013-09-27 | 2018-09-25 | Furukawa Electric Co., Ltd. | Heat-resistant silane crosslinked resin molded body and method of producing the same, heat-resistant silane crosslinkable resin composition and method of producing the same, silane master batch, and heat-resistant product using heat-resistant silane crosslinked resin molded body |
| US10304584B2 (en) | 2013-09-27 | 2019-05-28 | Furukawa Electric Co., Ltd. | Heat-resistant silane crosslinked resin molded body and method of producing the same, heat-resistant silane crosslinkable resin composition and method of producing the same, silane master batch, and heat-resistant product using heat-resistant silane crosslinked resin molded body |
| CN104610632A (en) * | 2015-01-14 | 2015-05-13 | 湖北祥源新材科技有限公司 | Colored high-performance and anti-static radiation cross-linked polyethylene foam material and preparation method thereof |
| TWI681994B (en) * | 2017-06-29 | 2020-01-11 | 美商陶氏全球科技有限責任公司 | Polyolefin composition |
| US11667735B2 (en) | 2017-06-29 | 2023-06-06 | Dow Global Technologies Llc | Polyolefin composition |
| CN107189176A (en) * | 2017-07-20 | 2017-09-22 | 合肥安力电力工程有限公司 | A kind of CABLE MATERIALS with fire protection flame retarding function and preparation method thereof |
| CN109593265A (en) * | 2018-12-14 | 2019-04-09 | 成都鑫成鹏高分子科技股份有限公司 | A kind of lower shrinkage silane CABLE MATERIALS and preparation method thereof |
| CN109593265B (en) * | 2018-12-14 | 2021-07-27 | 成都鑫成鹏高分子科技股份有限公司 | Low-shrinkage silane crosslinked cable material and preparation method thereof |
| CN115433400A (en) * | 2022-07-25 | 2022-12-06 | 广东金阳光电缆实业有限公司 | Process for producing halogen-free flame-retardant cable |
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