CN102280214A

CN102280214A - Electrical wire and method of making an electrical wire

Info

Publication number: CN102280214A
Application number: CN2011102408702A
Authority: CN
Inventors: 维杰伊.R.米塔尔; 维杰伊.雷加马尼; 克里斯托弗.雷克西厄斯; 佐藤匠; 邰向阳
Original assignee: SABIC Innovative Plastics IP BV
Current assignee: SABIC Global Technologies BV
Priority date: 2004-12-17
Filing date: 2005-11-29
Publication date: 2011-12-14
Anticipated expiration: 2025-11-29
Also published as: JP5313505B2; CN101080781A; JP2013239429A; KR20070087114A; EP1839317A1; WO2006065519A1; CN102280214B; EP1839317B1; ATE545138T1; KR100897655B1; CN101080781B; JP2008524829A

Abstract

An electrical wire and a method of making an electrical wire are disclosed. The electrical wire comprises a conductor and a covering. The covering comprises a thermoplastic composition comprising a poly(arylene ether), a polyolefin and a polymeric compatibilizer. The thermoplastic composition may further comprise a flame retardant.

Description

The manufacture method of electric wire and electric wire

It is on November 29th, 2005 that the present patent application is based on the applying date, and application number is 200580043406.7 (international application no is PCT/US2005/043048), and denomination of invention is divided an application for the patent application of " manufacture method of electric wire and electric wire ".

The cross reference of related application

The application requires the U.S. Provisional Application sequence number 60/637 of submission on December 17th, 2004,406,60/637,008,60/637,412 and 60/637, the U.S. Provisional Application sequence number 60/654 that on February 18th, 419 and 2005 submitted to, 247 priority, their full content is incorporated herein by reference herein.

Background of invention

Electric wire has been applied to use widely.In many application, conductor is surrounded by electric insulation thermoplasticity sheath.Though need be for insulating layer and thermoplastic sheath many and change along with the mode that will use electric wire and place, the especially for example application under the automobile protective cover of high voltage applications of major applications requires the insulating layer and thermoplastic sheath not have electric spark to leak (spark leaks).Electric spark leak since surround wire rod the insulation sheath defective for example pin hole cause.In the manufacturing of the electric wire that automobile is used, the electric spark of test wires leaks, and when finding that electric spark leaks, cuts off this wire rod and discard the part that comprises the electric spark leakage.The continuity of wire rod has been interrupted in the appearance that electric spark in the manufacture process leaks, and has reduced productivity ratio.Comprise the part that electric spark leaks because wire rod is cut to remove, caused the wire rod of multiple length.Usually these length of combination are to form the total length of packing and sale.

Electric wire is usually on comprising the bobbin of wire rod length overall tolerance or sell in the container, and described wire rod length overall tolerance is partly by the cross-sectional area decision of conductor.Take out electric wire to be used for for example automotive wire bundle of various goods from bobbin or container.For example, conductor cross-sectional area is 0.14mm ²To 1.00mm ²Electric wire, the total length of electric wire on bobbin can be 13,500 to 15,500 meters, and the quantity of separate cord can be 1 to 6 on the bobbin, wherein the minimum length of every wire is 150 meters.Comprise the bobbin of electric wire of plurality purpose separate cord or shorter length or container and cause lower productivity ratio and higher loss of yield when making goods by electric wire through regular meeting.

Be arranged in automobile electric wire below the cover of engine nacelle usually with the high-temperature insulation individual layer insulation that places on the copper conductors that does not coat.Thermoplastic polyester, crosslinked polyethylene and halogenated resin be thermal endurance, chemical resistance, anti-flammability and flexible needs during for example fluoropolymer and polyvinyl chloride have satisfied in this challenge environment high-temperature insulation for a long time.

The thermoplastic polyester insulating barrier has outstanding patience to gas and oil, is that machinery is tough and tensile, and the degraded of anti-copper catalysis, but can be because hydrolysis and premature failure.Also have been found that when the insulating layer exposing in the thermoplastic polyester insulated electric conductor is in hot salt brine and can split, and stand to lose efficacy when the humidity temperature cycles changes (cycling) when it.

More and more be desirably in the use that reduces in the insulating barrier or eliminate halogenated resin, because they have negative effect to environment.In fact, many countries begins the use that requirement reduces halogenated materials.But, because many wire rods apply extrusion device be based on halogenated resin for example the specification of polyvinyl chloride build, so any substitution material must be handled in the mode that is similar to polyvinyl chloride.

Crosslinked polyethylene provides high-temperature insulation like a bomb, but along with the progress to the demand of automobile electric wire, this success may be difficult to keep.Along with more electronic device is used for the modern means of communication, the wiring amount in the automobile increases.The overall diameter that the sharp increase of wiring has excited thickness of insulating layer that the automaker reduces by regulation and the littler conductor size of regulation to reduce electric wire.For example, the standard code of ISO 6722 is 2.5 square millimeters a conductor for cross-sectional area, and thinwalled insulation thickness is 0.35 millimeter, and the ultra-thin-wall insulation thickness is 0.25 millimeter.

When using crosslinked polyethylene, the insulation wall thickness reduce to cause difficulty.For crosslinked polyethylene, when when 150 ℃～180 ℃ furnace temperature is aging, thin thickness of insulating layer causes the short heat-resisting life-span.This has limited their heating grade (thermal rating).For example, the electric wire that has copper conductor and wall thickness and be the adjacent crosslinked polyetylene insulated layer of 0.75mm is flexible, and this insulating barrier can not split when around bent spindle being exposed to 150 ℃ after 3000 hours.But in having the similar electric wire of crosslinked polyetylene insulated layer that wall thickness is 0.25mm, this insulating barrier becomes fragile after 3000 hours being exposed to 150 ℃.The adverse effect that is produced by the demand of these extremely thin walls is owing to the degraded of copper catalysis, and this is the problem of extensively recognizing in the industry.

Therefore, need the method for electric wire and manufacturing electric wire, wherein said electric wire is suitable for automotive environment and does not contain the halogenation resin.

The invention summary

A kind of electric wire has satisfied above-mentioned needs, and this electric wire comprises:

Conductor (conductor); With

Place the sheath (covering) of this conductive surface, wherein this sheath comprises thermoplastic compounds, and this thermoplastic compounds comprises:

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein the cross-sectional area of this conductor is 0.15mm ²To 1.00mm ², the thickness of sheath is 0.15 to 0.25mm, in addition, it for total length 13,500 to 15,500 meters electric wire, the electric wire that is less than or equal to 6 independent length (individual length) is arranged, and the length of the electric wire of each independent length is more than or equal to 150 meters.Thermoplastic compounds also can comprise fire retardant.

In another embodiment, a kind of electric wire comprises:

Conductor; With

Sheath, this sheath comprises thermoplastic compounds, this thermoplastic compounds comprises:

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein sheath places conductive surface; With

Wherein, for 2500 to 15,500 meters electric wire, have smaller or equal to 5 electric sparks and leak.

In another embodiment, the method for manufacturing electric wire comprises:

Melting mixing is gathered (arylene ether), polyolefin and polymer compatibilizer to form first mixture;

Melt filteration first mixture is by having first filter that diameter is 20 microns to 150 microns perforate, to form first mixture that filters;

The mixture that melt filteration first is filtered is by having second filter that diameter is 20 microns to 150 microns perforate, to form second mixture that filters;

Second mixture that filters is administered on the conductor.

In another embodiment, the method for manufacturing electric wire comprises:

Melt filteration comprises poly-(arylene ether), the composition of polyolefin and polymer compatibilizer to be to form the composition that filters;

The composition that filters is administered on the conductor to form electric wire, and wherein this electric wire has per 2500 to 15,500 meters electric wires and is less than or equal to 3 electric spark and leaks.

In another embodiment, sheath comprises thermoplastic compounds, and wherein thermoplastic compounds comprises:

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein, comprise that the electric wire of the sheath that places conductive surface has smaller or equal to 5 electric sparks leakages for 2500 to 15,500 meters electric wire.Thermoplastic compounds also can comprise fire retardant.

In another embodiment, comprise the sheath of thermoplastic compounds, wherein this thermoplastic compounds comprises:

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein thermoplastic compounds is substantially free of visible particle shape impurity.Thermoplastic compounds also can comprise fire retardant.

In another embodiment, comprise that the sheath of thermoplastic compounds is made by the following method, this method comprises:

Melting mixing is gathered (arylene ether), polyolefin and polymer compatibilizer to form mixture;

This mixture of melt filteration passes through filter.

The present invention includes:

1. 1 kinds of electric wires of execution mode, it comprises:

Conductor; With

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein this sheath places conductive surface;

Wherein the cross-sectional area of this conductor is 0.15mm ²To 1.00mm ², the thickness of sheath is 0.15 to 0.25mm; And

Wherein, the electric wire that is less than or equal to 6 independent length is arranged, and the length of the electric wire of each independent length is more than or equal to 150 meters for 13,500 to 15,500 meters electric wire.

2. 1 kinds of electric wires of execution mode, it comprises:

Conductor; With

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein this sheath places conductive surface;

Wherein the cross-sectional area of this conductor is 0.30mm ²To 1.30mm ², the thickness of sheath is 0.15 to 0.35mm; And

Wherein, the electric wire that is less than or equal to 6 independent length is arranged, and the length of the electric wire of each independent length is more than or equal to 150 meters for 8,500 to 14,500 meters electric wire.

3. 1 kinds of electric wires of execution mode, it comprises:

Conductor; With

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein this sheath places conductive surface;

Wherein the cross-sectional area of this conductor is 1.20mm ²To 2.10mm ², the thickness of sheath is 0.29 to 0.36mm; And

Wherein, the electric wire that is less than or equal to 6 independent length is arranged, and the length of the electric wire of each independent length is more than or equal to 150 meters for 5,000 to 7,100 meters electric wire.

4. 1 kinds of electric wires of execution mode, it comprises:

Conductor; With

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein this sheath places conductive surface;

Wherein the cross-sectional area of this conductor is 2.90mm ²To 4.50mm ², the thickness of sheath is 0.3 to 0.8mm; And

Wherein, the electric wire that is less than or equal to 6 independent length is arranged, and the length of the electric wire of each independent length is more than or equal to 150 meters for 2,500 to 5,000 meters electric wire.

5. 1 kinds of electric wires of execution mode, it comprises:

Conductor; With

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein this sheath places conductive surface; And

Wherein, have to be less than or equal to 5 electric sparks leakages for 2,500 to 15,500 meters electric wire.

6. 1 kinds of methods of making the sheath of electric wire or conductor of execution mode, it comprises:

Melting mixing is gathered (arylene ether), polyolefin and polymer compatibilizer, to form first mixture;

Second mixture that filters is administered on the conductor.

7. 1 kinds of methods of making electric wire of execution mode, it comprises

Melt filteration comprises poly-(arylene ether), the composition of polyolefin and polymer compatibilizer, to form the composition that filters;

The composition that filters is administered on the conductor to form electric wire, and wherein this electric wire has per 2,500 to 15,500 meters electric wires and is less than or equal to 5 electric spark and leaks.

8. 1 kinds of sheaths of execution mode, it comprises thermoplastic compounds, wherein thermoplastic compounds comprises:

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Comprising the electric wire that places the sheath on the conductor,, there is the electric spark that is less than or equal to 5 to leak for 2,500 to 15,500 meters electric wire.

9. 1 kinds of sheaths that comprise thermoplastic compounds of execution mode, wherein this thermoplastic compounds comprises:

(i) poly-(arylene ether);

(ii) polyolefin; With

(iii) polymer compatibilizer,

Wherein thermoplastic compounds is substantially free of visible particle shape impurity.

The sheath of 10. 1 kinds of conductors of execution mode, wherein sheath comprises the thermoplastic compounds of being made by following method, this method comprises:

This mixture of melt filteration passes through filter.

The sheath of 11. 1 kinds of conductors of execution mode, wherein this sheath comprises the thermoplastic compounds of being made by following method, this method comprises:

Melt filteration first mixture is by first filter;

The mixture that melt filteration first is filtered is by second filter, to form second mixture that filters.

The sheath of execution mode 12. execution modes 11, wherein to have diameter be 20 microns to 150 microns perforate to first filter, it is 20 microns to 150 microns perforate that second filter has diameter, and perhaps all to have diameter be 20 microns to 150 microns perforate to first and second filters.

The sheath of execution mode 13. execution modes 11, wherein this sheath has thickness, and second filter has maximum gauge and is less than or equal to half the perforate of sheath thickness.

Each electric wire or sheath in execution mode 14. aforementioned embodiments, wherein conductor comprises single cord material or multi cord material.

Each electric wire or sheath in execution mode 15. aforementioned embodiments, wherein polyolefin is selected from the combination of polypropylene, high density polyethylene (HDPE) and polypropylene and high density polyethylene (HDPE).

Each electric wire or sheath in execution mode 16. aforementioned embodiments, wherein polymer compatibilizer comprises block copolymer, described block copolymer has the block for controlled distribution copolymer.

Each electric wire or sheath in execution mode 17. aforementioned embodiments, wherein polymer compatibilizer comprises first block copolymer and second block copolymer, wherein aryl alkylene content is more than or equal to 50 weight % of the first block copolymer total weight in first block copolymer, and aryl alkylene content is less than or equal to 50 weight % of the second block copolymer total weight in second block copolymer.

Each electric wire or sheath in execution mode 18. aforementioned embodiments, wherein polymer compatibilizer comprises diblock copolymer and triblock copolymer.

Each electric wire or sheath in execution mode 19. aforementioned embodiments, wherein polymer compatibilizer comprises polypropylene-polystyrene graft copolymer.

Each electric wire or sheath in execution mode 20. aforementioned embodiments, wherein thermoplastic compounds also comprises fire retardant.

Each electric wire or sheath in execution mode 21. aforementioned embodiments, wherein in the thermoplastic compounds polyolefin content by weight less than poly-(arylene ether) content amount by weight, based on the total weight of polyolefin and poly-(arylene ether).

Description of drawings

Fig. 1 is the diagram of wire cross-section.

Fig. 2 and 3 is the perspective views with electric wire of a plurality of layers.

Detailed Description Of The Invention

In this specification and claim, will be with reference to many terms, it will be defined as having following implication.

Unless context spells out in addition, singulative " ", " a kind of " and " being somebody's turn to do " (" a ", " an " and " the ") comprise plural indication thing.

" optional " or " randomly " is meant that incident or the situation next described can take place or can not take place, and this description comprises the situation that situation that this incident takes place and this incident do not take place.

Narrate the end points combination independently of all scopes of same feature, and comprise described end points.Be expressed as " greater than " or " less than " value comprise described end points, for example " greater than 3.5 " comprise value 3.5.

The standard of the ISO 6722 of indication is the version in the 15 days December in 2002 of this standard herein.

Because some reasons, poly-(arylene ether)/polyolefin blends unlikely selects to be used for the polymer sheath of electric wire.In the application of the composition of these types through being usually used in the requirement rigidity, but it has been generally acknowledged that application examples such as the electric wire that is not suitable for requiring flexibility.In addition, as described here, poly-(arylene ether) of poly-(arylene ether)/polyolefin blends is dispersed in the polyolefin matrix.As if because the degradation problem of copper catalysis in the known polyolefins, the composition that has a polyolefin matrix unlikely is successfully applied in the environment of degradation problem of copper catalysis.And when poly-(arylene ether) was exposed to the temperature of the glass transition temperature (Tg) that is higher than it, it tended to form particle and gel, and this can increase the possibility that the defective in the polymer sheath causes electric spark to leak.

The conductor that manufacturing has seldom or do not have a coating that electric spark leaks for example method of electric wire comprises: usually at melt mixing equipment for example in complex extruder or the banbury, melting mixing (mixing (compounding)) is used to form the component that the thermoplastic compounds of polymer sheath is used.In one embodiment, poly-(arylene ether), polymer compatibilizer and polyolefin are by the while melting mixing.In another embodiment, poly-(arylene ether), polymer compatibilizer and optional a part of polyolefin are melted mixing to form first molten mixture.Then, polyolefin or remaining polyolefin further with the first molten mixture melting mixing to form second molten mixture.Selectively, poly-(arylene ether) and a part of polymer compatibilizer can be melted mixing to form first molten mixture, then the polymer compatibilizer of polyolefin and remainder further with the first molten mixture melting mixing to form second molten mixture.

Aforementioned melting mixing process can be finished under the situation of not separating first molten mixture, perhaps can finish by separating first molten mixture.Can use one or more melt mixing equipments in these processes, each melt mixing equipment comprises one or more types.In one embodiment, some component of the thermoplastic compounds of formation sheath can be introduced into and be used for the extruder melting mixing of coated conductor.

When polymer compatibilizer comprises two kinds of block copolymers, a kind of aryl alkylene content is more than or equal to 50 weight %, when second kind aryl alkylene content is less than or equal to 50 weight %, poly-(arylene ether) and aryl alkylene content can be melted mixing forming first molten mixture more than or equal to the block copolymer of 50 weight %, and polyolefin and aryl alkylene content be less than or equal to 50 weight % block copolymer can with the first molten mixture melting mixing to form second molten mixture.

That is well understood in field polymer alloy and manufacturing thereof is the same, the adding method and the position of optional fire retardant, common kind (identity) and for example solid or liquid decision of physical property by fire retardant.In one embodiment, for example a part of polyolefin of one of component of fire retardant and thermoplastic compounds combines to form concentrate, and this concentrate mixes with remaining component melts then.

Poly-(arylene ether), polymer compatibilizer, polyolefin and optional fire retardant be at the glass transition temperature more than or equal to poly-(arylene ether), but the temperature that is lower than polyolefinic degradation temperature is melted mixing.For example, poly-(arylene ether), polymer compatibilizer, polyolefin and optional fire retardant can still may surpass this scope in short-term 240 ℃ to 320 ℃ extruder temperature melting mixing in the melting mixing process.In this scope, temperature can be more than or equal to 250 ℃, perhaps more specifically, and more than or equal to 260 ℃.Also in this scope, temperature can be less than or equal to 310 ℃, perhaps more specifically, is less than or equal to 300 ℃.

After some or all of components was melted mixing, molten mixture can be melted filtration and have a filter that diameter is 20 microns to 150 microns perforate by one or more.In this scope, perforate can have and is less than or equal to 130 microns, perhaps more specifically is less than or equal to 110 microns diameter.Also in this scope, perforate can have more than or equal to 30 microns, perhaps more specifically more than or equal to 40 microns diameter.

Can use any suitable melt filteration system or equipment that can remove granule foreign from molten mixture.In one embodiment, melt is filtered by single melt filtration system.Also can consider a plurality of fondant filter systems.

The melt filtering system that is fit to comprises the filter of being made by various materials, and described material is such as but not limited to the combination of sintering metal, metallic sieve or sieve, fiber metal felt, pottery or previous materials etc.Available especially filter is the sintered metal filter that shows high flexibility, comprises Pall Corporation and Martin Kurz ﹠amp; Company, the sintering metal bolting silk web filter (sintered wire mesh filter) that Inc. makes.

Can use the fondant filter of random geometry, it includes but not limited to taper shape, pleated (pleated), rod (candle), heap, flat, rolled, netted, boxlike, pack disc and aforesaid combination etc.According to the size of different parameters such as extruder, required productivity ratio and required particle filtration degree, the selection of geometry can change.Exemplary constituent material comprises stainless steel, titanium, nickel and other metal alloys.Can use the wire cloth (wire fabric) of different type of weaves, comprise the combination of plain weave weave, Holland (dutch) weave, grid weave (square), twill weave and weave.Available especially is the filter that is designed so that internal volume minimizes and reduces flow area and stand repeatedly clean cycle.

Melt filtering system can comprise periodic or continuous screen cloth replacing filter or intermittent filter.For example, screen cloth replacing filter can comprise the band screen web filter that slowly enters melt flows path in the extruder continuously.Melt blend this filter of flowing through, and this filter collects the granulometric impurity in this melt, because filter bag periodically or is continuously upgraded by new band portion, these impurity are taken out of outside the extruder by it.

In one embodiment, the maximum gauge of the perforate of filter is less than or equal to half of the sheath thickness that will be administered on the conductor.For example, if the electric wire sheath has 200 microns thickness, the maximum gauge of filter openings is less than or equal to 100 microns so.

The minimum dimension of filter openings depends on many variablees.Less filter openings can cause the bigger pressure of the upstream side of filter.Therefore, must select filter openings and method of operation to prevent the unsafe pressure of upstream side.In addition, use filter openings can cause filter upper reaches and dirty bad flowing simultaneously less than 20 microns filter.The bad mobile time of staying that may prolong the molten mixture of some part.The long time of staying can cause the formation and the increase of particle in the composition, and these particles can cause electric spark to leak when being administered to conductor.

In one embodiment, the mixture of melt filteration passes die head, and with drawing stretching granulation (strand pelletization) or the granulation of granulation underwater method.The material of granulation can be packaged, storage and transportation.In one embodiment, particle is packaged in the polybag that is lined with metal forming, is generally Polypropylene Bag, or is lined with in the paper bag of metal forming.Basically can find time to be equipped with all air in the bag of particle.

In one embodiment, thermoplastic compounds is substantially free of visible granule foreign.Visible particle or " black splotch " are just usually not need to amplify for the visible dark color of human eye or coloured particle, and have 40 microns or bigger average diameter.Though can not needing to amplify just range estimation, some discover average diameter less than 30 microns particle, but other people only can discover average diameter greater than 40 microns particle, term " visible particles ", " visible particle " and " black splotch ", when being used for pointing out concrete average diameter herein and not, be meant that average diameter is 40 microns or bigger particle.As used herein, term " is substantially free of visible particulate contamination " when being used for thermoplastic compounds, be meant that 5 of formation are of a size of 75mm * 50mm and thickness is the test print (plaque) of 3mm when composition is injection molding, and when these test the black splotch of prints from the visual inspection with the naked eye of all sides, the sum of the black splotch of all 5 test pieces is less than or equal to 100, perhaps more specifically, is less than or equal to 70, perhaps even more specifically, be less than or equal to 50.

In one embodiment, pellet is melted and with suitable method is for example extrusion coated said composition is administered on the conductor to form electric wire.For example, can use the coating extruder (coating extruder) that screw rod, crosshead, sieve plate (breaker plate), distributor, nozzle (nipple) and die head are installed.The molten thermoplastic composition forms and places conductor sheath on every side.Extrusion coatedly use the combination of single conical mould head, biconial die head, other suitable die head or die head that conductor is placed in the center, and avoid die lip to produce (die lip build up).

In one embodiment, composition is administered to the sheath that places conductive surface on the conductor with formation.Additional layer can be administered on the sheath.

In one embodiment, said composition is administered to having between conductor and the sheath on the conductor of one or more insert layers, places the sheath of conductive surface with formation.For example, optional adhesion promotion can be placed between conductor and the sheath.In another embodiment, can before using sheath, use the matal deactivator coated conductor.In another embodiment, insert layer comprises thermoplasticity or thermoset composition, and it foams in some cases.

Conductor can comprise single cord material or multi cord material.In some cases, the multi cord material can be by harness (bundled), twisting (twisted) or braiding (braided) to form conductor.In addition, conductor can have different shape, and is for example circular or oval.Conductor can be the conductor that is used to transmit signal of any kind.Exemplary signal comprises light, electricity and electromagnetism.Glass fibre is an example of optical conductor.Suitable electric conductor includes but not limited to, copper, aluminium, lead and comprise the alloy of one or more aforementioned metal.Conductor also can be conductive ink or paste.

The cross-sectional area of conductor and the thickness variable of sheath, and common final use decision by electric wire.This electric wire can be used as electric wire, and it includes but not limited to the wire rod of wire rod, electric power wire rod (wire for electric power), equipment wire rod, information communication wire rod, electric car (electric car) and ship that for example automobile electrical automobile fitting line (harness wire), household electrical appliance use, aircraft etc.In one embodiment, the conductor of coating is an optical cable, and can be used in internal application (in the building), applications (building is outer) or inside and outside application.Exemplary application comprises data transmission network and sound transmission network for example Local Area Network and telephone network.

In some embodiments, the drying thermoplastic composition may be useful before extruding applying.Exemplary drying condition is 60～90 ℃ of dryings 2～20 hours.In addition, in one embodiment, in extruding the applying process, thermoplastic compounds is melted filtration, before sheath forms, is 20 microns to 150 microns filter by one or more opening diameters.In this scope, opening diameter can be more than or equal to 30 microns, perhaps more specifically, and more than or equal to 40 microns.Also in this scope, opening diameter can be less than or equal to 130 microns, perhaps more specifically, is less than or equal to 110 microns.The coating extruder can comprise one or more aforesaid filters.

In one embodiment, in extruding the applying process, thermoplastic compounds is melted filtration, before sheath forms, is less than or equal to half filter of the sheath thickness that will be administered on the conductor by one or more perforate maximum gauges.For example, if the electric wire sheath has 200 microns thickness, the maximum gauge of filter openings is less than or equal to 100 microns so.

In another embodiment, the mixture of the melt filteration of melting mixing manufacturing does not carry out granulation.And be to use the coating extruder of connecting with melting mixing device (be generally and mix extruder), the mixture of melt filteration is directly formed the sheath of conductor.The coating extruder can comprise one or more aforesaid filters.

Colorant concentrate (color concentrate) or masterbatch can be added in the composition before extruding applying.When using the colorant concentrate, its common amount is for being less than or equal to 3 weight %, based on the total weight of composition.In one embodiment, not chloride, bromine of dyestuff that uses in the colorant concentrate and/or pigment and fluorine.As skilled in the art to understand, the color of composition may influence the final color of acquisition before adding the colorant concentrate, and in some cases, it may be favourable using bleaching agent and/or colour stabilizer.Bleaching agent and colour stabilizer are known in the art and can have bought.

The extruder temperature of extruding in the applying process is less than or equal to 320 ℃ usually, perhaps more specifically, is less than or equal to 310 ℃, perhaps more specifically, is less than or equal to 290 ℃.In addition, regulate processing temperature with melt composition that enough flowabilities are provided to provide sheath to conductor, temperature for example is higher than the fusing point of thermoplastic compounds, perhaps more specifically than at least 10 ℃ of the fusing point height of thermoplastic compounds.

Extrude after the applying, use the combination of water-bath, water spray, air injection or one or more aforementioned cooling meanss to cool off electric wire usually.Exemplary bath temperature is 20～85 ℃.Water can be deionized water, also it can be removed by filter impurity.As mentioned above, use the electric spark leakage of checking electric wire at line method (in-line method).The illustrative methods that the test electric spark leaks comprises the conductor that uses electric wire as grounding electrode, make electric wire near or pass charged electrode, make electric wire contact with charged electrode.When the polymer sheath on the electric wire comprises that defective for example when pin hole or crack, produces and detect arc light between the conductor of charged electrode and electric wire.Exemplary charged electrode comprises pelletron (bead chain) and brush.Can use alternating current or direct current to charge according to the final use of wire rod and all related industries specifications of wire rod to electrode.Voltage can be determined by the those of ordinary skill in electric spark leak test field.The frequency of using depends on load capacity, also can be determined by the those of ordinary skill in electric spark leak test field.Spark test equipment can be from for example Clinton Instrument Company, and Beta LaserMike and Zumbach have bought.

When detecting electric spark, cut off electric wire to remove the electric wire part that electric spark leaks.Therefore each electric spark leakage part produces the electric wire of a new length.After having accepted the electric spark leak detection, electric wire can be wrapped on bobbin or the similar equipment.Exemplary speed of wrap is the speed of 50 meters per minutes (m/min) to 1500m/min.Electric wire can be placed in the container that has or do not have bobbin or similar devices.Can make up several line lengths to constitute in the container or the wire rod total length on bobbin or the similar devices.Place the electric wire total length on container or bobbin or the similar devices to depend on the cross-sectional area of conductor and the thickness of sheath usually.

The length of the electric wire between electric spark leaks is important.If the container of electric wire comprises several length less than 150 meters section (length), electric wire is may service efficiency low, and this is because electric wire makes in a continuous manner and is used for constructing various goods, for example wire harness etc.Must the breaks in production flow process to begin a new wire segment.In addition, if each container has more than 6 wire segment independently, the use of electric wire also is inefficient so.Therefore, the quantity and the frequency of electric spark leakage all are important.

Therefore, be clear that, thermoplastic compounds must be applied on the wire rod with stable manner, have minimum or do not have electric spark to leak, thereby make that not having the minimum length of the electric wire of electric spark leakage is 150 meters when using when being suitable for the electric spark leak test method test electric wire of electric wire type, perhaps more specifically, 250 meters, perhaps even more specifically, 500 meters.Electric spark leaks and can cause as pin hole, particulate matter etc. by defective such as the slit in the wire rod sheath for example of the defective in the sheath.

Thermoplastic compounds be introduced or be derived to defective can by coating process (covering process).Defective may by in the coating process because insufficient cleaning of coating extruder introduce, if perhaps the operation of coating extruder stops to make thermoplastic compounds to form gel and black splotch for a long time and introduces.The residual substance of being stayed in the extruder by preceding once the coating may form the particle that causes defective and electric spark to leak.Can reduce or eliminate the defective that is incorporated in the thermoplastic compounds by part and the melt filteration thermoplastic compounds behind the thorough cleaning coating extruder especially filter.

Similarly, the part after cleaning melt mixing equipment, the especially filter rinsed can reduce or eliminate particulate matter and the gel that is produced by the residue that formerly uses that comes from complex extruder.

The cross section of exemplary electric wire is referring to Fig. 1.Fig. 1 shows the sheath 4 that places on the conductor 2.In one embodiment, sheath 4 comprises the thermoplastic compounds of foaming.The perspective view of exemplary electric wire is shown in Fig. 2 and 3.Fig. 2 show place the sheath 4 on the conductor 2 that comprises the multi cord material and place sheath 4 and conductor 2 on optional additional layer 6.In one embodiment, sheath 4 comprises the thermoplastic compounds of foaming.Conductor 2 also can comprise single conductor.Fig. 3 shows the sheath 4 that places on plain conductor 2 and the insert layer 6.In one embodiment, insert layer 6 comprises the composition of foaming.Conductor 2 also can comprise the multi cord material.

In one embodiment, to have cross-sectional area be 0.15mm to electric wire ²To 1.10mm ²Conductor, thickness is 0.15 to 0.25mm sheath, and is 13 for total length, 500 to 15,500 meters electric wire has to be less than or equal to 6 independent length, perhaps more specifically, be less than or equal to 4 independent length, perhaps even more specifically, be less than or equal to 3 independent length, and each independent length is more than or equal to 150 meters, perhaps more specifically, and more than or equal to 250 meters, perhaps even more specifically, more than or equal to 500 meters.As used herein, independent length is meant the single length of the electric wire with two ends.

In another embodiment, to have cross-sectional area be 0.30mm to electric wire ²To 1.30mm ²Conductor, thickness is 0.19 to 0.31mm sheath, and is 8 for total length, 500 to 14,000 meters electric wire has to be less than or equal to 6 independent length, perhaps more specifically, be less than or equal to 4 independent length, perhaps even more specifically, be less than or equal to 3 independent length, and each independent length is more than or equal to 150 meters, perhaps more specifically, and more than or equal to 250 meters, perhaps even more specifically, more than or equal to 500 meters.

In another embodiment, to have cross-sectional area be 1.20mm to electric wire ²To 2.10mm ²Conductor, thickness is 0.29 to 0.36mm sheath, and is 5 for total length, 000 to 7,100 meter electric wire has to be less than or equal to 6 independent length, perhaps more specifically, be less than or equal to 4 independent length, perhaps even more specifically, be less than or equal to 3 independent length, and each independent length is more than or equal to 150 meters, perhaps more specifically, and more than or equal to 250 meters, perhaps even more specifically, more than or equal to 500 meters.

In another embodiment, to have cross-sectional area be 2.90mm to electric wire ²To 4.50mm ²Conductor, thickness is 0.3 to 0.8mm sheath, and is 2 for total length, 500 to 5,000 meters electric wire has to be less than or equal to 6 independent length, perhaps more specifically, be less than or equal to 4 independent length, perhaps even more specifically, be less than or equal to 3 independent length, and each independent length is more than or equal to 150 meters, perhaps more specifically, and more than or equal to 250 meters, perhaps even more specifically, more than or equal to 500 meters.

Thermoplastic compounds described herein comprises two-phase at least, and promptly polyene hydrocarbon phase and poly-(arylene ether) are mutually.The polyene hydrocarbon phase is a continuous phase.In some embodiments, poly-(arylene ether) is dispersed in the polyene hydrocarbon phase mutually.The good compatible physical property that improves of can causing mutually, it is included in the higher impact strength of low temperature and room temperature, better heat ageing, better anti-flammability and bigger tensile elongation.What accept usually is that the form of composition is represented the degree or the quality of compatibility.The particle little, relative uniform-dimension that spreads all over poly-(arylene ether) of whole composition area distribution is equably represented good compatible effect (good compatibilization).

Thermoplastic compounds described herein is substantially free of for example polystyrene (being also referred to as high impact polystyrene or HIPS) of polystyrene or modified rubber of alkenyl aromatic resin." be substantially free of " to be defined as and comprise less than 10 weight % (wt%), or more specifically less than 7wt%, or more specifically less than 5wt%, or even more specifically less than the alkenyl aromatic resin of 3wt%, based on the total weight of poly-(arylene ether), polyolefin and block copolymer.In one embodiment, composition does not contain alkenyl aromatic resin fully.Surprisingly, the existence meeting of alkenyl aromatic resin influences the compatible effect between poly-(arylene ether) phase and the polyene hydrocarbon phase unfriendly.

In one embodiment, said composition has 8,000 to less than 18,000 kg/cm ²(kg/cm ²) flexural modulus of (800 to less than 1800 MPas (MPa)).In this scope, flexural modulus can be more than or equal to 10,000kg/cm ²(1000MPa), perhaps, more specifically, more than or equal to 12,000kg/cm ²(1200MPa).In this scope, flexural modulus can be less than or equal to 17,000kg/cm equally ²(1700MPa), perhaps, more specifically, be less than or equal to 16,000kg/cm ²(1600MPa).Flexural modulus described herein is determined by the speed of using ASTM D790-03 and 1.27mm/min.The flexural modulus value is the mean value of three samples.The sample that flexural modulus is used uses 600-700 kilogram/cm ²Injection pressure and 15 to 20 seconds retention time, originating from Toyo Machinery ﹠amp; The Plastar Ti-80G of Metal Co.LTD ₂Injection molding machine on form.Remaining condition of moulding is shown in the table 1.

Table 1

Baking temperature (℃)	80
		Drying time (in hour)	4
Barrel zone temperature
		1	240
2	250
		3	260
4	260
		DH	260
Mold temperature	80

In one embodiment, electric wire satisfies or surpasses the requirement of the standard of ISO 6722, is meant particularly wearing and tearing, rank A, B, the requirement of the heat-resistant aging of C, chemical resistance and environment circulation change.

As used herein, " poly-(arylene ether) " comprises the construction unit of a plurality of general formulas (I):

Wherein, for each construction unit, each Q ¹And Q ²The halo oxyl that separates halogen and oxygen atom independently at least for hydrogen, halogen, uncle or secondary low alkyl group (alkyl that for example comprises 1 to 7 carbon atom), phenyl, haloalkyl, aminoalkyl, thiazolinyl alkyl, alkynyl alkyl, oxyl, aryl and two carbon atoms.In some embodiments, each Q ¹Be for example C of alkyl or phenyl independently _1-4Alkyl, each Q ²Be hydrogen or methyl independently.Poly-(arylene ether) can comprise the molecule with the end group that contains aminoalkyl, and described end group is usually located at the ortho position of hydroxyl.What also often occur is tetramethyl two benzoquinones (TMDQ) end groups, and it obtains from the reactant mixture that has tetramethyl two benzoquinones accessory substances usually.

Poly-(arylene ether) can be the form of homopolymers, copolymer, graft copolymer, ionomer or block copolymer, and the combination that comprises at least a aforementioned forms.Poly-(arylene ether) comprises polyphenylene ether, and it comprises and randomly makes up 2,3,6-trimethyl-1,2 of 4-phenylene ether units, 6-dimethyl-1,4-phenylene ether units.

Poly-(arylene ether) can be by oxidative coupling monohydroxy aromatic compounds for example 2,6-xylenol, 2,3, and 6-front three phenol and 2,6-xylenol and 2,3, the combination of 6-front three phenol prepares.Catalyst system is adopted in this coupling usually; Described catalyst system and catalyzing can comprise heavy metal compound for example copper, manganese or cobalt compound, makes up for example combination of secondary amine, tertiary amine, halide or two or more aforesaid compounds of various other materials usually.

In one embodiment, poly-(arylene ether) comprises poly-(arylene ether) of end-blocking.Terminal hydroxyl can be by for example acylation reaction end-capping reagent end-blocking.The end-capping reagent of selecting is preferably following end-capping reagent, and poly-(arylene ether) that it causes less reactive reduces thus or prevent at high temperature in the course of processing that polymer chain is crosslinked and form gel or blackspot.Suitable end-capping reagent comprises ester of the derivative of salicylic acid, ortho-aminobenzoic acid or its replacement for example etc.; Salicylic ester especially salicylic carbonate and linear polysalicylates is preferred.As used herein, term " salicylic ester " comprises wherein carboxyl, hydroxyl or the two all esterified compound.Suitable salicylate comprises for example salicylic acid aryl ester such as phenyl salicytate, acetylsalicylic acid, salicylic carbonate and polysalicylates, and it comprises linear polysalicylates and cyclic compound for example disalicylide, three salicylides (trisalicylide).In one embodiment, end-capping reagent is selected from salicylic carbonate and polysalicylates, especially linear polysalicylates and the combination that comprises a kind of aforesaid compound.Poly-(arylene ether) of exemplary end-blocking and their preparation have description No. the 4th, 760,118, the United States Patent (USP) that licenses to White etc. with licensing in the 6th, 306, No. 978 of Braat etc.

Also think, can reduce the amount of the group that is present in the aminoalkyl end-blocking in poly-(arylene ether) chain with polysalicylates end-blocking poly-(arylene ether).Aminoalkyl is the result who uses the oxidative coupling of amine in the process of making poly-(arylene ether).The aminoalkyl that is in the terminal hydroxy group ortho position of poly-(arylene ether) at high temperature decomposes easily.This decomposition be considered to cause uncle or the regeneration of secondary amine and the generation of quinone methides end group, this so may produce 2,6-dialkyl group-1-hydroxyphenyl end group.Poly-(arylene ether) that comprise aminoalkyl with the polysalicylates end-blocking is considered to remove this amino, the terminal hydroxy group and the 2-hydroxy-n that cause the end-blocking of polymer chain, N-alkyl benzene formamide (2-hydroxy-N, N-alkylbenzamine) formation of (salicylamide (salicylamide)).Amino remove and end-blocking provides a kind of to high temperature more stable poly-(arylene ether), cause thus in the course of processing of poly-(arylene ether) catabolite still less.

Poly-(arylene ether) can have 3,000 to 40, the number-average molecular weight and 5 of 000 gram/mole (g/mol), 000 to 80, the weight average molecular weight of 000g/mol, it uses monodisperse polystyrene mark thing (40 ℃ SDVB gels) by gel permeation chromatography and has a sample of 1 milligram of concentration of every milliliter of chloroform definite.The combination of poly-(arylene ether) or multiple poly-(arylene ether) has the initial intrinsic viscosity more than or equal to 0.25dl/g, measures in 25 ℃ of chloroforms.Initial intrinsic viscosity be defined as with the inherent viscosity of poly-(arylene ether) before other component melts of composition is mixed, the inherent viscosity that final response viscosity is gathered (arylene ether) after being defined as and mixing with other component melts of composition.As one of ordinary skill in the understanding, the added value of the viscosity of poly-(arylene ether) can be up to 30% after melting mixing.The percentage that increases can calculate by (final response viscosity-initial intrinsic viscosity)/initial intrinsic viscosity.When using two initial intrinsic viscosity, determine accurately than the precise characteristics viscosity of poly-(arylene ether) that more or less will depend on use and desired final physical character.

Poly-(arylene ether) that be used to make thermoplastic compounds can be substantially free of visible particulate contamination.In one embodiment, poly-(arylene ether) is substantially free of diameter greater than 15 microns particulate contamination.As used herein, term " is substantially free of visible particulate contamination " when being used to gather (arylene ether), is meant to be dissolved in 50 milliliters of chloroform (CHCl ₃) in the sample of 10 grams poly-(arylene ether), when in light box (light box), detecting by an unaided eye, demonstrate and be less than 5 visible spots.Macroscopic particle normally diameter greater than 40 microns particle.As used herein, term " is substantially free of diameter greater than 15 microns particulate contamination " and is meant and is dissolved in 400 milliliters of CHCl ₃In the sample of 40 grams poly-(arylene ether), the number of particle that is of a size of 15 microns in every gram is less than 50, this is by Pacific Instruments ABS2 analyzer, measurement of average value based on 5 samples obtains, the dissolved polymers material that described each sample is 20 ml vols makes described polymer material flow through analyzer with the flow velocity (± 5%) of 1 milliliter of per minute.

Thermoplastic compounds comprises poly-(arylene ether) with respect to composition total weight 30 to 65 weight % (wt%) amount.In this scope, the amount of poly-(arylene ether) can be more than or equal to 40wt%, perhaps more specifically, and more than or equal to 45wt%.Also in this scope, the amount of poly-(arylene ether) can be less than or equal to 55wt%.

Polyolefinic universal architecture is C _nH _2n, and comprise polyethylene, polypropylene and polyisobutene.Exemplary homopolymers comprises polyethylene, LLDPE (linear low density polyethylene (LLDPE)), HDPE (high density polyethylene (HDPE)) and MDPE (medium density polyethylene) and isotactic polypropylene.The vistanex of this universal architecture and their preparation method are well-known in the art, for example in United States Patent (USP) 2,933,480,3,093,621,3,211,709,3,646,168,3,790,519,3,884,993,3,894,999,4,059,654, in 4,166,055 and 4,584,334 description is arranged.

Also can use for example copolymer of ethene and alhpa olefin such as propylene, octene and 4-methylpentene-1 of polyolefinic copolymer, and the copolymer of the copolymer of ethene and one or more rubber and propylene and one or more rubber.Ethene and C ₃-C ₁₀The copolymer of monoolefine and non-conjugated diene is called the EPDM copolymer herein, also is suitable.The suitable C that is used for the EPDM copolymer ₃-C ₁₀The example of monoolefine comprises propylene, 1-butylene, 2-butylene, 1-amylene, 2-amylene, 1-hexene, 2-hexene and 3-hexene.Suitable diene comprises 1,4-hexadiene and monocycle and many cyclic diolefines.Ethene and other C ₃-C ₁₀The mol ratio of monoolefine monomer can be 95: 5 to 5: 95, and the amount that diene units exists is 0.1 to 10mol%.The EPDM copolymer can be functionalized with the disclosed electrophilic group that is used to be grafted on the polyphenylene ether in acetyl group or the United States Patent (USP) 5,258,455.

Thermoplastic compounds can comprise the combination of the combination of single homopolymers, homopolymers, single copolymer, copolymer or comprise homopolymers and the combination of copolymer.

In one embodiment, polyolefin is selected from the combination of polypropylene, high density polyethylene (HDPE) and polypropylene and high density polyethylene (HDPE).Polypropylene can be homo-polypropylene or polypropylene copolymer.The copolymer of polypropylene and rubber or block copolymer are called impact-resistant modified polypropylene sometimes.This copolymer is out-phase normally, and the segment (section) with sufficiently long each component is having amorphous phase and crystalline phase simultaneously.In addition, polypropylene can comprise homopolymers and copolymer combination, have different melt temperatures homopolymers combination or have the combination of the homopolymers of different melt flow rate.

In one embodiment, polypropylene comprises for example isotactic polypropylene of crystalline polypropylene.Crystalline polypropylene is defined as degree of crystallinity content (crystallinity content) more than or equal to 20%, perhaps more specifically, and more than or equal to 25%, perhaps even more specifically, the polypropylene more than or equal to 30%.Degree of crystallinity can be measured by differential scanning calorimetric (DSC).

In some embodiments, polypropylene has more than or equal to 134 ℃, perhaps more specifically, and more than or equal to 140 ℃, perhaps even more specifically, more than or equal to 145 ℃ melt temperature.

Polypropylene has greater than 0.4g/10min and is less than or equal to the melt flow rate (MFR) (MFR) of 15g/10min (g/10min).In this scope, melt flow rate (MFR) can be more than or equal to 0.6g/10min.Also in this scope, melt flow rate (MFR) can be less than or equal to 10, perhaps more specifically, is less than or equal to 6, perhaps more specifically is less than or equal to 5g/10min.Melt flow rate (MFR) can be used pulverous or granular polypropylene according to ASTM D1238, in the load of 2.16kg and 230 ℃ temperature measuring.

High density polyethylene (HDPE) can be ceridust or polyethylene and ethylene copolymers.In addition, high density polyethylene (HDPE) can comprise homopolymers and copolymer combination, have different melt temperatures homopolymers combination or have the different melt flow rate and usually density be 0.941-0.965g/cm ³The combination of homopolymers.

In some embodiments, high density polyethylene (HDPE) has more than or equal to 124 ℃, perhaps more specifically, and more than or equal to 126 ℃, perhaps even more specifically, more than or equal to 128 ℃ melt temperature.

High density polyethylene (HDPE) has more than or equal to 0.10g/10min and is less than or equal to the melt flow rate (MFR) (MFR) of 15g/10min (g/10min).In this scope, melt flow rate (MFR) can be more than or equal to 1.0g/10min.Also in this scope, melt flow rate (MFR) can be less than or equal to 10, perhaps more specifically, is less than or equal to 6, perhaps more specifically is less than or equal to 5g/10min.Melt flow rate (MFR) can be used polyethylene powdery or granular according to ASTM D1238, in the load of 2.16kg and 190 ℃ temperature measuring.

Said composition can comprise the polyolefin of 15 to 35 weight % (wt%) amount, with respect to the total weight of composition.In this scope, polyolefinic amount can be more than or equal to 17wt%, perhaps more specifically, and more than or equal to 20wt%.Also in this scope, polyolefinic amount can be less than or equal to 33wt%, perhaps more specifically, is less than or equal to 30wt%.

In one embodiment, polyolefin comprises high density polyethylene (HDPE) (HDPE) and polypropylene, and the amount of HDPE (by weight) is less than polyacrylic amount (by weight).

In one embodiment, the amount (by weight) of polyolefin existence is less than the amount (by weight) of poly-(arylene ether).

Polymer compatibilizer is resin and the additive that improves the compatibility between polyene hydrocarbon phase and poly-(arylene ether) phase.Polymer compatibilizer comprises block copolymer, polypropylene-polystyrene graft copolymer and the block copolymer as described below and the combination of polypropylene-polystyrene graft copolymer.

As herein with whole specification in used, " block copolymer " is meant single combination of planting block copolymer or multiple block copolymer.Block copolymer comprises that at least one contains the block of aryl alkylene repetitive (A) and at least one contains the block (B) of repetitive unit of alkylidene.Block (A) and arrangement (B) can be linear structure or so-called radially far-end block structure (radial teleblock structure) with side chain.The A-B-A triblock copolymer has two block A that contain the aryl alkylene repetitive.The side aryl moiety of aryl alkene unit can be monocycle or many rings, and can have substituting group in any available position of loop section.Suitable substituents comprises the alkyl with 1 to 4 carbon atom.Exemplary aryl alkene unit is the phenyl ethylidene shown in the formula II:

As long as the amount of aryl alkene unit surpasses the amount of alkylidene unit, block A just can further comprise the alkylidene unit with 2 to 15 carbon atoms.

B block comprises for example combination of ethylidene, propylidene, butylidene or two or more aforementioned groups of repetitive unit of alkylidene with 2 to 15 carbon atoms.As long as the amount of alkylidene unit surpasses the amount of aryl alkene unit, B block just can further comprise aryl alkene unit.

Block A can have the identical or different molecular weight with other block A separately.Similarly, B block can have the molecular weight identical or different with other B block separately.Block copolymer can functionalised by the reaction with the alpha-beta unsaturated carboxylic acid.

In one embodiment, the B block comprises aryl alkene unit and has the copolymer of the alkylidene unit of 2 to 15 carbon atoms that described alkylidene unit is the combination of ethylidene, propylidene, butylidene or two or more aforementioned groups for example.The B block can further comprise some unsaturated non-aromatics carbon-carbon bonds.

The B block can be the copolymer of controlled distribution." controlled distribution " is defined as and is meant a kind of molecular structure as used herein, it lacks the well-defined block of arbitrary monomer, wherein " little block (runs) " of any given single monomer has the maximum number mean value of Unit 20, this shows by only there being a single glass transition temperature (Tg) between the Tg of two homopolymers, or shows by the proton magnetic resonance (PMR) method.When the B block comprised the copolymer of controlled distribution, each A block may have 3,000 to 60, the mean molecule quantity of 000g/mol, and each B block may have 30,000 to 300, the mean molecule quantity of 000g/mol, this measures by light scattering technique.When the B block is the copolymer of controlled distribution, each B block comprise at least one be rich in the petiolarea adjacent of alkylidene unit with the A block and be rich in aryl alkene unit not with A block adjacent areas.The total amount of aryl alkene unit is 15 to 75 weight %, based on the total weight of block copolymer.The weight ratio of alkylidene unit and aryl alkene unit can be 5: 1 to 1: 2 in the B block.Exemplary block copolymers has further open in U.S. Patent application the 2003/181584th, and can buy with trade (brand) name KRATON from Kraton Polymers.Exemplary specification is A-RP6936 and A-RP6935.

The aryl alkylene repetitive is produced by for example cinnamic polymerization of aryl alkene monomer.Repetitive unit of alkylidene by diene for example the hydrogenation of the unsaturated unit of the butadiene repetition of deriving produce.Butadiene can comprise 1,4-butadiene and/or 1,2-butadiene.The B block also can comprise some undersaturated non-aromatics carbon-carbon bonds.

Exemplary block copolymer comprises polyphenylene ethene-poly-, (ethylene/propene)-polyphenylene ethene, (polyphenylethylene-poly, (ethylene/propylene)-polyphenylethylene), (sometimes be written as polystyrene-poly, (ethylene/propene)-polystyrene) and polyphenylene ethene-poly-, (ethylene/butylene)-polyphenylene ethene, (polyphenylethylene-poly, (ethylene/butylene)-polyphenylethylene), (sometimes be written as polystyrene-poly, (ethylene/butylene)-polystyrene).

In one embodiment, polymer compatibilizer comprises two kinds of block copolymers.The aryl alkylene content of first block copolymer is more than or equal to 50 weight %, based on the total weight of first block copolymer.The aryl alkylene content of second block copolymer is less than or equal to 50 weight %, based on the total weight of second block copolymer.The combination of exemplary block copolymer is that styrene-content is first polystyrene-poly (ethylene/butylene)-polystyrene of 15 weight % to 40 weight %, total weight based on block copolymer, with styrene-content be second polystyrene-poly (ethene-butylene)-polystyrene of 55 weight % to 70 weight %, based on the total weight of block copolymer.Aryl alkylene content can have been bought with trade (brand) name TUFTEC from Asahi greater than the exemplary block copolymers of 50 weight %, and has for example H1043 of specification title, and some can be from the specification of Kuraray with trade (brand) name SEPTON acquisition.Aryl alkylene content can have been bought with trade (brand) name KRATON from Kraton Polymers less than the exemplary block copolymers of 50 weight %, and has for example specification title of G-1701, G-1702, G-1730, G-1641, G-1650, G-1651, G-1652, G-1657, A-RP6936 and A-RP6935.

In one embodiment, polymer compatibilizer comprises triblock copolymer and diblock copolymer.

In some embodiments, block copolymer has 5,000～1, and the number-average molecular weight of 000,000 gram/mole (g/mol) uses polystyrene mark thing to measure by gel permeation chromatography (GPC).In this scope, number-average molecular weight can be at least 10,000g/mol, perhaps more specifically, and at least 30,000g/mol, perhaps even more specifically, and at least 45,000g/mol.Also in this scope, number-average molecular weight can be preferably up to 800,000g/mol, perhaps more specifically, and up to 700,000g/mol, perhaps even more specifically, and up to 650,000g/mol.

Polypropylene-polystyrene graft copolymer is defined as the graft copolymer with propylene polymer main chain and one or more styrene polymer grafting herein.Forming the main chain of polypropylene-polystyrene graft copolymer or the amphoteric polymeric material of matrix is (a) Noblen; (b) random copolymer of propylene and alkene, this alkene is selected from ethene and C ₄-C ₁₀Alkene, condition is, when alkene is ethene, the ethylene contents of polymerization is about 10 weight % at the most, preferably about at the most 4 weight %, and when alkene be C ₄-C ₁₀During alkene, the C of polymerization ₄-C ₁₀Olefin(e) centent is about 20 weight % at the most, preferably about at the most 16 weight %, and (c) propylene and at least two kinds are selected from ethene and C ₄-C ₁₀The random terpolymer of the alkene of alpha-olefin, condition are the C of polymerization ₄-C ₁₀Olefin(e) centent is about 20 weight % at the most, preferably about at the most 16 weight %, and when ethene is one of alkene, and the ethylene contents of polymerization is about 5 weight % at the most, preferably about at the most 4 weight %; Or (d) homopolymers or the random copolymer of propylene, it carries out impact-resistant modified in reactor with ethylene-propylene monomer rubber and physical mixed, the ethylene-propylene monomer rubber content of the polymer of modification is about 5 to about 30 weight %, the ethylene contents of rubber is about 7 to about 70 weight %, and preferred about 10 to about 40 weight %.C ₄-C ₁₀Alkene comprises the C of straight chain and branching ₄-C ₁₀Alpha-olefin is the 1-butylene for example, 1-amylene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 3,4-dimethyl-1-butylene, 1-heptene, 1-octene, 3-methyl-hexene etc.Noblen and impact-resistant modified Noblen are preferred amphoteric polymeric materials.Though be not preferred, be about 2 also can be used as amphoteric polymeric material to ethylene-propylene-diene monomer rubber of about 8 weight % impact-resistant modified Noblen and random copolymer with diene content.Suitable diene comprises bicyclopentadiene, 1,6-hexadiene, ENB etc.

Be used in reference to the term " styrene polymer " of the graft polymers on the main chain that is present in amphoteric polymeric material in polypropylene-polystyrene graft copolymer, be meant the homopolymers of (a) styrene or ring-alkylated styrenes, this ring-alkylated styrenes is for having at least one C ₁-C ₄The ring-alkylated styrenes of the alkyl ring substituents of straight chain or branching is especially to ring-alkylated styrenes; (b) has (a) monomer copolymer each other of arbitrary proportion; (c) at least a (a) monomer and its Alpha-Methyl derivative copolymer of AMS for example, wherein the Alpha-Methyl derivative account for copolymer about 1 to about 40 weight %.

Polypropylene-polystyrene graft copolymer can comprise about 10 to about 90 weight % propylene polymer main chain and the about 90 styrene polymer grafting to about 10 weight %.In this scope, propylene polymer main chain can account for total graft copolymer at least about 20 weight %, and propylene polymer main chain can account for total graft copolymer up to about 40 weight %.Also in this scope, the styrene polymer grafting can account for total graft copolymer at least about 50 weight %, perhaps more specifically, exist at least about the amount of 60 weight %.

The preparation of polypropylene-polystyrene graft copolymer is for example licensing to DeNicola, in the United States Patent (USP) 4,990,558 of Jr. etc. description is arranged.Suitable polypropylene-polystyrene graft copolymer also is commercially available, for example from P1045H1 and the P1085H1 of Basell.

The amount that polymer compatibilizer exists is 2 to 30 weight % with respect to composition total weight.In this scope, polymer compatibilizer can perhaps more specifically exist with the amount more than or equal to 6 weight % with respect to the total weight of composition with more than or equal to 4 weight %.Also in this scope, polymer compatibilizer can exist with the amount that is less than or equal to 18 weight % with respect to the total weight of composition, perhaps more specifically, to be less than or equal to 16 weight %, perhaps even more specifically, exists with the amount that is less than or equal to 14 weight %.

Exemplary fire retardant comprises melamine (CAS No.108-78-1), melamine cyanurate (melamine cyanurate) (CAS No.37640-57-6), melamine phosphate (CAS No.20208-95-1), melamine pyrophosphate (CAS No.15541-60-3), polyphosphoric acid melamine (CAS#218768-84-4), melam, melem (melem), cyanogen urea acid amides (melon), Firebrake ZB (CAS No.1332-07-6), boron phosphate, red phosphorus (CAS No.7723-14-0), organophosphorus ester, ammonium dihydrogen phosphate (CASNo.7722-76-1), diammonium hydrogen phosphate (CAS No.7783-28-0), phosphonate ester (CAS No.78-38-6 and 78-40-0), the metal dialkyl phosphinates, APP (CAS No.68333-79-9), the combination of low-melting glass (low melting glasses) and two or more aforementioned fire retardants.

Exemplary organophosphorus ester flame-proof agent includes but not limited to, phosphate, and it comprises the combination of the phenyl of the phenyl of phenyl, replacement or phenyl and replacement; Based on two aryl phosphate esters of resorcinol, for example resorcinol two-diphenyl phosphoester; And based on those organophosphorus esters of bis-phenol for example bisphenol-A two-diphenyl phosphoester.In one embodiment, organophosphorus ester (for example is selected from tricresyl phosphate (alkyl benzene) ester, CASNo.89492-23-9 or CAS No.78-33-1), resorcinol is two-diphenyl phosphoester (for example, CASNo.57583-54-7), bisphenol-A two-diphenyl phosphoester (for example, CAS No.181028-79-5), triphenyl phosphate (for example, CAS No.115-86-6), the mixture of tricresyl phosphate (cumene) ester (for example, CAS No.68937-41-7) and two or more aforementioned organophosphorus esters.

In one embodiment, organophosphorus ester comprises two aryl phosphate esters of general formula III:

Wherein, R, R ⁵And R ⁶Independently of one another for having the alkyl of 1 to 5 carbon atom, R ¹-R ⁴Independently for having alkyl, aryl, aralkyl or the alkaryl of 1 to 10 carbon atom; N is 1 to 25 integer; With s1 and s2 be 0 to 2 integer independently.In some embodiments, OR ¹, OR ², OR ³And OR ⁴Independently derived from phenol, monoalkyl phenol, dialkyl group phenol or trialkyl phenol.

Understand easily as those skilled in the art institute, two aryl phosphate esters are derived from bis-phenol.Exemplary bis-phenol comprises 2, two (4-hydroxyphenyl) propane (so-called bisphenol-A), 2 of 2-, two (the 4-hydroxy-3-methyl phenyl) propane of 2-, two (4-hydroxyphenyl) methane, two (4-hydroxyl-3,5-xylyl) methane and 1, two (4-hydroxyphenyl) ethane of 1-.In one embodiment, bis-phenol comprises bisphenol-A.

Organophosphorus ester can have different molecular weight, this feasible amount that is difficult to determine different organophosphorus esters used in the thermoplastic compounds.In one embodiment, the content of phosphorus is 0.8 weight % to 1.2 weight % with respect to composition total weight in the organophosphorus ester.

In being present in thermoplastic compounds, the amount of fire retardant is enough to make electric wire, when the flame propagation rules that define in the standard according to ISO 6722 are tested, has the fray-out of flame time that is less than or equal to 70 seconds.

In one embodiment, fire retardant comprises organophosphorus ester, and the amount of its existence is 5 to 18 weight % (wt%) with respect to composition total weight.In this scope, the amount of organophosphorus ester can be more than or equal to 7wt%, perhaps more specifically, and more than or equal to 9wt%.Also in this scope, the amount of organophosphorus ester can be less than or equal to 16wt%, perhaps more specifically, is less than or equal to 14wt%.

In addition, composition also can randomly comprise for example antioxidant of various additives; Particle mean size is less than or equal to filler and the reinforcing agent of 10 μ m, for example silicate, TiO ₂, fiber, glass fibre, glass marble, calcium carbonate, talcum and mica; Release agent; The UV absorbent; Stabilizer is light stabilizer etc. for example; Lubricant; Plasticizer; Pigment; Dyestuff; Colouring agent; Antistatic agent; Blowing agent (blowing agent); Foaming agent (foaming agent); Matal deactivator and comprise the combination of one or more aforementioned additive.

Further specify composition and electric wire by following non-limiting example.

Embodiment

Use listed material preparation following examples in the table 2.

Table 2

Prepare thermoplastic compounds by each component of melting mixing in double screw extruder.PPE and block copolymer add at charging aperture, and PP adds in second perforate of catchment extruder.Organophosphorus ester adds with fluid injector at the latter half of extruder.The preparation said composition is not used filter (not having screen cloth), or is used one or two to have different bore size, the filter melt filteration as shown in table 4 and 5.End at extruder uses the granulation of line material with this material granulation.Composition is shown in Table 3.

Extrude with conductor form electric wire before, 80 ℃ of following drying thermoplastic compositions 3-4 hour.Conductor is to have 0.2 square millimeter of (mm ²) copper cash of conductor size.Use the linear velocity of 250m/min to make electric wire.Preheat thermoplastic compounds at 100 ℃, and it is expressed on 275 ℃ the conductor, do not use filter (not having screen cloth), perhaps apparatus is just like the filter melt filteration of the bore size (in micron) shown in table 4 and 5.Sheath has the thickness of 0.2mm (table 4) and 0.15mm (table 5).Use 5 kilovolts (KV) on 1250 meters length, use high-frequency AC spark test instrument (model HF-ISA/BD-12 derives from The Clinton Instrument Company, Clinton, Connecticut) electric spark of test wires leaks.Every group of electric spark of creating conditions leaks number shown in table 4 and 5.

Table 3

Table 4

* Comparative Examples

Table 5

* Comparative Examples

From table 4 and table 5 as can be seen, in the melting mixing process, extrude in the applying process or melting mixing and to extrude filtration in the applying process has seldom or do not have electric spark to leak for manufacturing electric wire be important, especially along with the reduction of sheath thickness, all the more so.

Though described the present invention with reference to several execution modes, it should be appreciated by those skilled in the art that and to make various variations, and equivalent can replace its composition, and not depart from scope of the present invention.In addition, can make many versions,, and not depart from its base region so that concrete situation or material are adapted to instruction of the present invention.Therefore, expectation the invention is not restricted to conduct and carries out the disclosed embodiment of best mode of the present invention, and the present invention will comprise all execution modes in the scope that falls into claims.

The full content of the patent of all references, patent application and other list of references is incorporated herein by reference herein.

Claims

1. method of making electric wire, it comprises:

Melting mixing is gathered (arylene ether), polyolefin and polymer compatibilizer, and to form first mixture, described polymer compatibilizer is selected from polypropylene-polystyrene graft copolymer; Comprise the block copolymer of at least one block A and at least one B block, described block A comprises the aryl alkylene repetitive, and described B block comprises repetitive unit of alkylidene; And the combination of aforementioned graft copolymer and block copolymer;

Melt filteration first mixture is by having the filter of perforate, to form the mixture that filters; And the composition that filters is administered on the conductor to form the sheath on the conductor, the maximum gauge of the perforate of wherein said filter is less than or equal to half of described sheath thickness.

2. the process of claim 1 wherein that described mixture comprises that 30-55wt% gathers (arylene ether), 15-35wt% polyolefin and 2-30wt% polymer compatibilizer, based on the total weight of described composition.

3. the process of claim 1 wherein that described electric wire has per 2,500 to 15,500 meters electric wires and is less than or equal to 5 electric spark leakage.

4. the process of claim 1 wherein that conductor comprises single cord material or multi cord material.

5. the process of claim 1 wherein that polyolefin is selected from the combination of polypropylene, high density polyethylene (HDPE) and polypropylene and high density polyethylene (HDPE).

6. the process of claim 1 wherein that polymer compatibilizer comprises block copolymer, described block copolymer has the block for controlled distribution copolymer.

7. the method for claim 1, wherein polymer compatibilizer comprises first block copolymer and second block copolymer, wherein aryl alkylene content is more than or equal to 50 weight % of the first block copolymer total weight in first block copolymer, and aryl alkylene content is less than or equal to 50 weight % of the second block copolymer total weight in second block copolymer.

8. the process of claim 1 wherein that polymer compatibilizer comprises diblock copolymer and triblock copolymer.

9. the process of claim 1 wherein that polymer compatibilizer comprises polypropylene-polystyrene graft copolymer.

10. the process of claim 1 wherein that thermoplastic compounds also comprises fire retardant.

11. the process of claim 1 wherein that polyolefin content by weight is less than poly-(arylene ether) content by weight, based on the total weight of polyolefin and poly-(arylene ether) in the thermoplastic compounds.