CN106232647B - Silane Grafted haloflex, its manufacturing method and the insulated electric conductor and cable that have used the polyethylene - Google Patents
Silane Grafted haloflex, its manufacturing method and the insulated electric conductor and cable that have used the polyethylene Download PDFInfo
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- CN106232647B CN106232647B CN201580022355.3A CN201580022355A CN106232647B CN 106232647 B CN106232647 B CN 106232647B CN 201580022355 A CN201580022355 A CN 201580022355A CN 106232647 B CN106232647 B CN 106232647B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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Abstract
The present invention provides a kind of Silane Grafted haloflex, its manufacturing method, the insulated electric conductor and cable for having used the polyethylene, and the Silane Grafted haloflex has the high degree of cross linking, obtained by the way that methylacryloyl Silane Grafted to be copolymerized.The present invention provides a kind of Silane Grafted haloflex, will have using peroxide by H2C=C (CH3) the silane compound graft copolymerization of methylacryloyl that indicates of-CO- forms in haloflex; when the molal quantity of silane compound being set as x, the molal quantity of peroxide being set as to y, the quantity of oxygen contained in peroxide and the key of oxygen is set as α; x/2 α y is 1.5 or more 20.0 hereinafter, the gel fraction after crosslinking is 60% or more.
Description
Technical field
The present invention relates to Silane Grafted haloflex, its manufacturing method and the insulated electric conductors for having used the polyethylene
And cable.
Background technique
Haloflex be by using the methods of aqueous suspension method make as the polyethylene of raw material and chlorine have an effect from
And one of the thermoplastic elastomer (TPE) obtained.Haloflex has pliability, weatherability, oil resistivity, chemical resistance, fire-retardant
The extensive characteristic such as property, heat resistance, abrasion performance, is widely used as forming surrounding layer of cable etc. (hereinafter also referred to as sheath)
Material.
It is known usually in the case where forming sheath by haloflex, after haloflex is squeezed out, make chlorinated polyethylene
Alkene is crosslinked.As cross-linking method, carrying out extensively using silane compound (silane coupling agent) crosslinked with silicane (such as
Referring to patent document 1).
In crosslinked with silicane, firstly, by containing silane compound and peroxide in haloflex, thus in mistake
Silane compound graft copolymerization is formed into Silane Grafted haloflex in haloflex in the presence of oxide.Then, lead to
Crossing makes Silane Grafted haloflex contact and be crosslinked with water, to form crosslinked with silicane haloflex.
As silane compound, such as vinyltrimethoxysilane, vinyltriethoxysilane is being widely applied
Deng the silane compound with vinyl (hereinafter also referred to as vinyl silanes).But the volatility of vinyl silanes it is high and
With distinctive penetrating odor, thus there is not easy to handle such problems.Therefore, as the silane for replacing vinyl silanes
Compound, people are studying the silane compound with methylacryloyl, acryloyl group or styryl.Wherein, by
It is high in equal upper practicability in terms of cost, thus the silane compound with methylacryloyl is (hereinafter also referred to as metering system
Acyl silanes) it attracts attention.
Existing technical literature
Patent document
Patent document 1: the clear 50-35540 bulletin of Japanese Patent
Summary of the invention
The project solved is wanted in invention
In comparison methacryl base silane and vinyl silanes are not easy graft copolymerization in haloflex.Therefore,
Silane Grafted haloflex obtained from the copolymerization of methylacryloyl Silane Grafted is lower such ask there are the degree of cross linking
Topic.
The purpose of the present invention is to provide a kind of Silane Grafted haloflex, its manufacturing method, the polyethylene is used
Insulated electric conductor and cable, the Silane Grafted haloflex has the high degree of cross linking, by by methacryl base silane
Graft copolymerization and obtain.
The solution to the problem
An embodiment of the invention provides a kind of Silane Grafted haloflex, wherein will have using peroxide
Have by H2C=C (CH3) the silane compound graft copolymerization of methylacryloyl that indicates of-CO- forms in haloflex, will before
The molal quantity for stating silane compound is set as x, the molal quantity of aforementioned peroxide is set as to y, will be contained in aforementioned peroxide
When the quantity of the key of oxygen and oxygen is set as α, x/2 α y be 1.5 or more 20.0 hereinafter, crosslinking after gel fraction (gel
It fraction) is 60% or more.
Other embodiments of the present invention provide a kind of manufacturing method of Silane Grafted haloflex, include mistake
Oxide makes an addition to the addition process of haloflex, and has by adding into aforementioned haloflex by H2C=C
(CH3)-CO- indicate methylacryloyl silane compound, thus by aforementioned silane compounds graft copolymerization in aforementioned chlorine
Change the grafting process of polyethylene；In foregoing graft process, the molal quantity of aforementioned silane compounds is set as x, by aforementioned peroxide
When the molal quantity of compound is set as y, the quantity of oxygen contained in aforementioned peroxide and the key of oxygen is set as α, become according to x/2 α y
1.5 or more 20.0 modes below add aforementioned silane compounds, and foregoing graft work is carried out after by aforementioned addition process
Sequence.
Other embodiments of the present invention provide a kind of insulated electric conductor, and it includes conductors, the periphery to surround aforementioned conductor
The insulating layer that is arranged of mode, which is formed by Silane Grafted haloflex, which is benefit
To have with peroxide by H2C=C (CH3)-CO- indicate methylacryloyl silane compound graft copolymerization in chlorination
Polyethylene forms, and the molal quantity of aforementioned silane compounds is set as x, the molal quantity of aforementioned peroxide is set as to y, by aforementioned mistake
When the quantity of the key of oxygen and oxygen contained in oxide is set as α, x/2 α y be 1.5 or more 20.0 hereinafter, gel fraction be 60% with
On.
Other embodiments of the present invention provide a kind of cable, the side of the periphery it includes conductor, to surround aforementioned conductor
The insulating layer of formula setting, the surrounding layer being arranged in a manner of the periphery for surrounding aforementioned dielectric layer, the surrounding layer is by Silane Grafted chlorine
Change polyethylene to be formed, which is will have using peroxide by H2C=C (CH3)-CO- indicate first
The silane compound graft copolymerization of base acryloyl group is formed in haloflex, by the molal quantity of aforementioned silane compounds be set as x,
When being set as y by the molal quantity of aforementioned peroxide, the quantity of oxygen contained in aforementioned peroxide and the key of oxygen be set as α, x/2
α y is 1.5 or more 20.0 hereinafter, gel fraction is 60% or more.
The effect of invention
According to embodiment of the present invention, it provides and a kind of is connect with the high degree of cross linking and by methacryl base silane
Silane Grafted haloflex, its manufacturing method, the insulated electric conductor and cable for having used the polyethylene obtained from branch copolymerization.
Detailed description of the invention
Fig. 1 is the sectional view of cable involved in an embodiment of the invention.
Fig. 2 is the sectional view of insulated electric conductor involved in an embodiment of the invention.
Fig. 3 is the explanatory diagram for indicating the grafting process for having used extruder in the embodiment of the present invention.
Fig. 4 is the explanatory diagram for indicating the production process of the cable in the embodiment of the present invention.
Specific embodiment
The inventors of the present invention study the above subject, as a result, it has been found that, methacryl base silane and vinyl silanes phase
Comparatively speaking graft copolymerization is not easy in haloflex, i.e. grafting rate of the methacryl base silane on haloflex is low
The reason of be, methacryl base silane be easy react with the free radical generated in graft copolymerization.For this point, with
Under be specifically described.
In general, the graft copolymerization of silane compound is carried out by free radical.Specifically, firstly, by making chlorine
Change in polyethylene containing silane compound and peroxide and heated, peroxide is subjected to thermal decomposition to generate freedom
Base (such as oxygen radical).Oxygen radical generates the free radical of haloflex by capturing the hydrogen in haloflex.
Then, unsaturated bond (such as vinyl, methylacryloyl) possessed by the free radical and silane compound of haloflex
It is reacted, so that silane compound is by graft copolymerization in haloflex.In this way, the graft copolymerization of silane compound by by
Peroxide generate oxygen radical and start to react.
But in above-mentioned graft copolymerization, originally with the oxygen radical of chlorinated polyethylene alkene reaction sometimes with silanization
Object is closed to be reacted.That is, oxygen radical is consumed because reacting with silane compound sometimes.Therefore, oxygen radical and chlorination
The reaction of polyethylene is hindered, so that the free radical of haloflex is not likely to produce.As a result, silane compound is not
Can fully graft copolymerization is in haloflex so that the grafting rate of silane compound is lower.In particular, in silane compound
In, methacryl base silane due to it is in comparison high with the reactivity of oxygen radical with vinyl silanes etc. and be easy with
Oxygen radical is reacted, thus being grafted rate can be lower.If the grafting rate of silane compound in this way is lower, make silane
When graft CPE is crosslinked, the degree of cross linking can be lower.
The inventors of the present invention study the method for solving the problems, such as this, as a result, it has been found that, preferably added by peroxide
Methacryl base silane is added after haloflex, rather than methacryl base silane is added simultaneously with peroxide
Add.In the past, when peroxide and silane compound being made an addition to haloflex, for example, by addition make peroxide and silane
Solution obtained from compound dissolution, so that they be added simultaneously.But in the case where methacryl base silane, if
It adds with peroxide, then during being scattered in them in haloflex, is generated by peroxide simultaneously
As a result free radical leads to connecing for methacryl base silane so that peroxide is consumed with methylacryloyl silane reaction
Branch copolymerization is hindered.In contrast, in the case where adding methacryl base silane after being added to peroxide, due to
It can in advance disperse peroxide in haloflex, thus be able to suppress peroxide when dispersing methacryl base silane
The consumption of compound.As a result, can on haloflex graft copolymerization methacryl base silane well.Base of the present invention
It is completed in these opinions.
< an embodiment of the invention >
One embodiment of the present invention will be described below.
(1) Silane Grafted haloflex
The Silane Grafted haloflex of present embodiment is to utilize peroxide by the silane with methylacryloyl
Compound (methacryl base silane) graft copolymerization is obtained from haloflex.Silane Grafted haloflex is in molecule
There is the silylation from silane compound in chain, have and be crosslinked such structure and being reacted with water.Below to each
Ingredient is specifically described.
Haloflex, such as by by linear polyethylene (low density polyethylene (LDPE), high density polyethylene (HDPE) etc.) suspended dispersed
Yu Shuizhong and obtain aqueous suspension, chlorine is blown into the aqueous suspension and is obtained.About the chlorination degree of haloflex,
From the grafting rate for improving silane compound, that is, from the viewpoint of improving degree of cross linking when making its crosslinking, be preferably set to 25% with
Upper 45% hereinafter, be more preferably set as 30% or more 40% or less.
Silane compound has by H2C=C (CH3)-CO- indicate methylacryloyl.Methylacryloyl is and chlorination
The substituent group for the unsaturated bond that the free radical of polyethylene is reacted.Silane compound passes through methylacryloyl and chlorinated polyethylene
The free radical of alkene carries out reaction to which graft copolymerization is in haloflex.
In addition, silane compound has water-disintegrable silylation.In the chemical structure of Silane Grafted haloflex, lead to
It crosses silane compound graft copolymerization in haloflex to import silylation.Silylation makes Silane Grafted haloflex
When reacting and being crosslinked with water, silanol group is become by hydrolysis.Silanol group passes through dehydrating condensation (silanol condensation)
And form cross-linked structure.As silylation, such as can enumerate with the hydrolyzable knot such as halogen, alkoxy, acyloxy, phenoxy group
The silylation of structure.As the silylation with these hydrolyzable structures, such as halosilyl, alkoxy first silicon can be enumerated
Alkyl, acyloxysilyl, phenoxy group silicyl etc..
Specifically, 3- methacryloxypropyl trimethoxy silane, 3- methyl can be used as silane compound
Acryloxypropyl triethoxysilane, 3- methacryloxypropylmethyl dimethoxysilane, 3- methacryl
The methacryls base silanes such as oxygroup hydroxypropyl methyl diethoxy silane.
Peroxide is the substance for the graft copolymerization silane compound on haloflex.It, can as peroxide
It is using the hydrogen-taking capacity for capturing hydrogen from haloflex high and can be not easily deteriorated in haloflex and (be not easy dehydrochlorination)
Temperature is thermally decomposed and is generated the organic peroxide of oxygen radical.Since the deterioration initial temperature of haloflex is 200
DEG C or so, thus as peroxide, it is preferable to use 1 minute half life temperature is 120 DEG C or more 200 DEG C of organic peroxies below
Compound.It the use of 1 minute half life temperature is more preferably 150 DEG C or more 200 from the viewpoint of shortening graft reaction required time
DEG C organic peroxide below.It is explained, 1 minute half life temperature refers to that the half-life period of peroxide becomes 1 point
The temperature of clock.
Specifically, bis- (1- methyl-1s-phenylethyl) can be used, and (peroxidating two is different for peroxide as peroxide
Propyl benzene), 1,1- bis- (tert-butyl hydroperoxide) hexamethylene, t-butylperoxyisopropyl carbonic ester, t-amyl peroxy isopropyl
Carbonic ester, 2,5- dimethyl -2,5- two (tert-butyl hydroperoxide) hexamethylene, tert-butyl hydroperoxide 2- ethylhexyl carbonate etc..
They can be used alone a kind, can also be used in combination of two or more.In them, pair that 1 minute half life temperature is about 175 DEG C can be used
(1- methyl-1-phenylethyl) peroxide (so-called cumyl peroxide).
About silane compound and peroxide, the molal quantity of silane compound is set as x, by mole of peroxide
When number is set as y, the quantity of the key (peroxide bridge ,-O-O- key) of oxygen contained in peroxide and oxygen is set as α, x/2 α y is preferably
1.5 or more 20.0 hereinafter, more preferably 3 or more 9 or less.X/2 α y indicates the silane compound being matched in haloflex
The ratio of molal quantity and the molal quantity of the free radical (oxygen radical) generated by peroxide.If x/2 α y less than 1.5, due to
Insufficient tendency that there are free radicals for silane compound, thus be possible to silane compound can not be fully grafted
It is copolymerized in haloflex.On the other hand, if x/2 α y is more than 20.0, since there are free radicals relative to silane compound and
Speech becomes superfluous tendency, thus when making silane compound graft copolymerization, it is possible to the cross-linking reaction that can be not intended to.Cause
This, if x/2 α y is set as 1.5 or more 20 hereinafter, if the abundant graft copolymerization of silane compound can be made in haloflex, and
It is able to suppress cross-linking reaction when making its graft copolymerization.
For silane compound and peroxide, become 1.5 or more 20.0 or less such contents then if it is x/2 α y
It is not particularly limited.For example, relative to 100 mass parts of haloflex, the content of silane compound be preferably 1.0 mass parts with
Upper 10 below the mass.The content of peroxide be preferably 0.03 mass parts or more 3.0 below the mass.At this point, silane chemical combination
The molal quantity x of object is preferably 4.0 × 10-3~4.0 × 10-2In the range of, by the free radical (oxygen radical) of peroxide generation
2 α y of molal quantity be preferably 2.2 × 10-4~2.2 × 10-2In the range of.
In Silane Grafted haloflex, from the viewpoint of being effectively crosslinked it, it is anti-to preferably comprise promotion crosslinking
The silanol condensation catalyst answered.As silanol condensation catalyst, for example, magnesium, Gai Deng II race element, cobalt, iron etc. can be used
VIII group element, the metallic elements such as tin, zinc and titanium, the metallic compound comprising these elements.In addition, can be used octanoic acid, oneself
Metal salt, amine compound, acid of diacid etc..Specifically, two neodecanoic acid dioctyl tins, di lauric dibutyl can be used
Tin, dibutyltin diacetate, two sad dibutyl tins, stannous acetate, stannous octoate, lead naphthenate, zinc octoate, cobalt naphthenate etc.
Metal salt, the inorganic acids such as the amine compounds such as ethamine, dibutyl amine, hexylamine, pyridine, sulfuric acid, hydrochloric acid, toluenesulfonic acid, acetic acid, tristearin
The organic acids such as acid, maleic acid.
In addition, plasticizer, antioxidant (including age resister), carbon black can also be contained in Silane Grafted haloflex
Equal fillers, other additives such as fire retardant, lubricant, copper evil discoloration preventing agent, cross-linking aid, stabilizer.
(2) crosslinked with silicane haloflex
Crosslinked with silicane haloflex is and reacting above-mentioned Silane Grafted haloflex with water to be crosslinked
It obtains.About crosslinked with silicane haloflex, such as the gel fraction of the index as the degree of cross linking is 60% or more.If gel point
Number is less than 60%, then the degree of cross linking of crosslinked with silicane haloflex is lower, thus the surrounding layer (shield for example having for cable
Set), the mechanical properties such as tensile strength can not be obtained.From the viewpoint of the mechanical property for improving sheath etc., gel fraction it is upper
Limit value is not particularly limited.Gel fraction is more got higher, and the degree of cross linking is more got higher, then is formed in crosslinked with silicane haloflex more
Cross-linked structure, thus the mechanical property of sheath etc. shows raised tendency mostly.
Gel fraction is found out as described below.Firstly, the sample formed by crosslinked with silicane haloflex is immersed in two
In toluene, dimethylbenzene heating is made into its boiling.Thereafter, the undissolved sample remaining in dimethylbenzene is taken out (to be extracted with hot dimethylbenzene
Sample after taking), it is dried, measures the quality of the sample after hot xylene extraction.Then, by calculating hot dimethylbenzene
Sample mass extracted is relative to the ratio with the sample mass before hot xylene extraction, so as to find out crosslinked with silicane chlorination
The gel fraction of polyethylene.To be set as a with the sample mass before hot xylene extraction, will be with the sample after hot xylene extraction
When quality is set as b, gel fraction R is expressed from the next.
R (%)=(b/a) × 100
(3) manufacturing method of Silane Grafted haloflex
Then, the manufacturing method of above-mentioned Silane Grafted haloflex is illustrated.
(addition process)
Firstly, adding such as cumyl peroxide into haloflex as peroxide, heating mixing is carried out.It is logical
Mixing is crossed, disperses peroxide in haloflex.At this point, adding 0.03 matter relative to 100 mass parts of haloflex
3.0 peroxide below the mass of part or more is measured, the peroxide of 0.1 mass parts or more 1.2 below the mass is preferably added.
It is explained, temperature when mixing is preferably set to the degradation temperatures of haloflex or less.
(grafting process)
Then, into the haloflex for being dispersed with peroxide, the methacryl with methylacryloyl is added
Base silane carries out heating mixing.By being kneaded, it is scattered in methacryl base silane in haloflex.In grafting process
In, the molal quantity of silane compound is set as x, the molal quantity of peroxide is set as to y, by oxygen contained in peroxide and oxygen
The quantity of key when being set as α, preferably become 1.5 or more 20.0 modes below according to x/2 α y and add methacryl base silane.
For example, preferably adding the methacryl of 1.0 mass parts or more 10 below the mass relative to 100 mass parts of haloflex
Base silane.
By making an addition to methacryl base silane in haloflex, thus in the presence of peroxide by methyl
Acryl silane graft copolymerization forms Silane Grafted haloflex in haloflex.In the present embodiment, pass through by
Peroxide makes an addition to haloflex in advance and makes its dispersion, thus making methacryl base silane be scattered in chlorinated polyethylene
When alkene, it is able to suppress by the oxygen radical of peroxide generation and reacting for methacryl base silane.That is, can make by peroxide
The oxygen radical that compound generates efficiently is reacted with haloflex, efficiently generates the free radical of haloflex.It is as a result,
Make when using the methacryl base silane with high reactivity with oxygen radical, also can suitably graft copolymerization gather in chlorination
Ethylene.
Be explained, above-mentioned addition process and grafting process in, such as by using roller machine, extruder, pinch
The mixing reaction unit such as conjunction machine, mixing machine, autoclave, which be kneaded, to be preferred.In addition, compounding conditions, graft reaction condition (temperature,
Time etc.) it is not particularly limited.
(4) composition and manufacturing method of cable
In the following, the cable 1 to an embodiment of the invention is illustrated.Fig. 1 is an embodiment of the invention
The sectional view of related cable 1.
As shown in Figure 1, the cable 1 of present embodiment has conductor 10.As conductor 10, can be used by hypoxemia copper, nothing
The copper wire of the formation such as oxygen copper, copper alloy wire, it is twisted as the metal wire of the formation such as aluminium, silver or by metal wire made of be twisted together line.
The outer diameter of conductor 10 can be suitable for change according to the purposes of cable 1.
Insulating layer 11 is provided in a manner of the periphery of coated conductor 10.Insulating layer 11 is by always well known resin combination
Object, for example, the resin combination comprising ethylene propylene rubber is formed.The thickness of insulating layer 11 can be fitted according to the purposes of cable 1
Preferably change.
Surrounding layer 12 (sheath 12) is provided in a manner of by the periphery of insulating layer coating 11.Sheath 12 is by by connecing silane
Crosslinked with silicane haloflex obtained from branch haloflex is crosslinked is formed.Sheath 12 is 60% or more by gel fraction
Crosslinked with silicane haloflex formed, have the high degree of cross linking.
Cable 1 for example manufactures as follows.Firstly, preparing such as copper wire as conductor 10.Moreover, for example, using squeezing out
Machine squeezes out the resin combination comprising ethylene propylene rubber in a manner of the periphery of coated conductor 10, to form predetermined thickness
Insulating layer 11.Then, above-mentioned Silane Grafted chlorination is squeezed out according to predetermined thickness in a manner of by the periphery of insulating layer coating 11 to gather
Ethylene, to form sheath 12.Thereafter, by reacting the Silane Grafted haloflex to form sheath 12 with water, silicon is formed
The crosslinkable chlorinated polyethylene of alkane, so that sheath 12 be made to be crosslinked.Specifically, in the Silane Grafted chlorinated polyethylene for forming sheath 12
In alkene, the silylation in chemical structure is caused to be hydrolyzed and reacting with water, to become silanol group.Also, pass through
Silanol group carries out dehydrating condensation and combines, so that the strand of Silane Grafted haloflex is crosslinked, to form silicon
The crosslinkable chlorinated polyethylene of alkane.As a result, it is crosslinked sheath 12, to obtain the cable 1 of present embodiment.It is explained
It is when being crosslinked Silane Grafted haloflex, for example, being preferred under the atmosphere of 60 DEG C of saturated vapor.
The effect > of < embodiments of the present invention
According to the present embodiment, one or more effects as shown below are played.
(a) according to the present embodiment, grafting process is carried out after the addition process by peroxide.That is, pass through by
Peroxide makes an addition to haloflex, thereafter add methacryl base silane, thus make silane compound graft copolymerization in
Haloflex forms Silane Grafted haloflex.It is carried out making methacryl base silane be scattered in haloflex
When graft copolymerization, since peroxide is made an addition to haloflex in advance and makes its dispersion, it is thus possible to inhibit by peroxidating
The oxygen radical that object generates is reacted with methacryl base silane.That is, can by make oxygen radical and haloflex into
Row reaction, to efficiently generate the free radical of haloflex.Thereby, it is possible to suitably be grafted methacryl base silane
It is copolymerized the grafting rate that can be improved the base silane of the methacryl in Silane Grafted haloflex in haloflex.Cause
This, when being crosslinked Silane Grafted haloflex, can obtain gel fraction is 60% or more, with the high degree of cross linking
Crosslinked with silicane haloflex.
In contrast, as in the past, if methacryl base silane and peroxide are made an addition to chlorinated polyethylene simultaneously
Alkene passes through the oxygen radical and methylacryloyl silicon generated by peroxide then when making them be scattered in haloflex
Alkane reacts, so that peroxide is consumed.Therefore, it is impossible to make methacryl base silane effectively graft copolymerization in chlorination
Polyethylene.As a result, leading to the grafting rate of methacryl base silane reduces, hand over Silane Grafted haloflex
Gel fraction when connection will be less than 60%.
(b) according to the present embodiment, graft copolymerization is carried out making methacryl base silane be scattered in haloflex
When, peroxide is made an addition into haloflex in advance and makes its dispersion.It therefore, can be by the peroxide that is dispersed in chlorination
It is equably generated free radicals in polyethylene.Then, by being homogeneously dispersed in methacryl base silane in haloflex,
So as to make methacryl base silane, equably graft copolymerization imports in the chemical structure of haloflex, and equably
Silylation.As a result, since haloflex can be made equably to be crosslinked, it is thus possible to reduce the friendship of crosslinked with silicane haloflex
Connection degree deviation (locality crosslinking), and improve the mechanical properties such as elongation.In addition, can reduce because of haloflex locality mistake
Degree be crosslinked and convex grain (Star Block) for generating etc. caused by bad order.
The molal quantity of silane compound (c) according to the present embodiment, is set as x, the molal quantity of peroxide is set as to y,
When the quantity of oxygen contained in peroxide and the key of oxygen is set as α, x/2 α y is 1.5 or more 20.0 or less.If x/2 α y is 1.5
More than, then by relative to methacryl base silane enough and fully supply free radical, so as to make methacryl
Base silane effectively graft copolymerization in haloflex.If x/2 α y be 20.0 hereinafter, if by relative to methylacryloyl silicon
Alkane supplies free radical according to not superfluous mode, to be able to suppress chlorination when being copolymerized methylacryloyl Silane Grafted
Polyethylene carries out cross-linking reaction.Therefore, if x/2 α y is set as 1.5 or more 20 hereinafter, if silane compound can be made fully to connect
Branch copolymerization is able to suppress cross-linking reaction when carrying out graft copolymerization in haloflex.
(d) according to the present embodiment, volatility height is substituted by using methacryl base silane and there is irritation
The vinyl silanes of smell so as to improve operating environment, and can steadily carry out grafting process.In addition, methyl
Acryl silane boiling point, flash-point compared with vinyl silanes is high, thus is able to suppress hair in the manufacturing processes such as grafting process
It lights a fire calamity.
(e) according to the present embodiment, the sheath of cable is by making Silane Grafted haloflex be crosslinked, by coagulating
The crosslinked with silicane haloflex that glue score is 60% or more is formed.Therefore, cable has high mechanical strength.
< other embodiments of the present invention >
More than, an embodiment of the invention is specifically illustrated, but the present invention is not only restricted to above-mentioned embodiment, it can
It is suitable for change in the range of not departing from its main idea.
It is middle to the surrounding layer 12 (sheath 12) in cable 1 to use Silane Grafted haloflex in above-mentioned embodiment
The case where be illustrated, but not limited thereto.For example, it is also possible to make in the insulating layer 11 of insulated electric conductor 2 as shown in Figure 2
With Silane Grafted haloflex.In the case, it in the same manner as when forming sheath 12 using above-mentioned embodiment, is leading
The periphery of body 10 squeezes out Silane Grafted haloflex and forms insulating layer 11, and insulating layer 11 is made to contact with water and carry out crosslinkable silane
Connection is preferred.
Embodiment
In the following, illustrating the embodiment of the present invention.
Material used in embodiment and comparative example is as follows.
Haloflex (Mooney viscosity (ML1+4) at 121 DEG C: 55, melts heat: less than 1.0J/g): Hangzhou section benefit
Chemical Co., Ltd's system " CM352L "
Hydrotalcite: Kyowa Chemical Industry Co., Ltd's system " Magcellar (マ グ セ ラ ー) 1 "
Epoxidised soybean oil: NOF Corp's system " Newcizer 510R "
Polyethylene wax (PE wax, molecular weight: 2800): Mitsui Chemicals, Inc's system " Hi-wax NL-200 "
Peroxide (cumyl peroxide): NOF Corp's system " DCP "
Silane compound (3- methacryloxypropyl trimethoxy silane): Shin-Etsu Chemial Co., Ltd's system
“KBM-503”
Silane compound (3- methacryloxypropyl): Shin-Etsu Chemial Co., Ltd's system
“KBE-503”
Plasticizer (naphthene series processing oil): Idemitsu Kosen Co., Ltd.'s system " NP-24 "
Sulfur antioxidant (4,4 '-thiobis (3 methy 6 tert butyl phenol)): the emerging chemical industry strain formula of imperial palace
Commercial firm's system " Nocrac 300R "
Amine antioxidant (2,2,4 trimethyl 1,2 dihydroquinoline polymer): the emerging chemical industry strain formula of imperial palace
Commercial firm's system " Nocrac 224 "
Fire retardant (antimony trioxide): Sumitomo Metal Mining Co., Ltd's system " antimony trioxide "
Carbon (FEF carbon black): Asahi Carbon Co. Ltd. system " Asahi Carbon 60G "
Lubricant (the double oleamides of ethylene): Nippon Kasei Chemical Company's system " Slipax-O "
Silanol condensation catalyst (two neodecanoic acid dioctyl tins): Nitto Kasei Co., Ltd's system " Neostan U-
830”
(1) modulation of chlorinated polyethylene composition
(embodiment 1)
In the present embodiment, it successively carries out the addition process of peroxide, be grafted the addition process of process and filler,
To modulate the chlorinated polyethylene composition containing Silane Grafted haloflex.
[the addition process of peroxide]
Firstly, relative to powdered 100 mass parts of haloflex, being added as stabilizer using 8 inch roller machines
6 mass parts of hydrotalcite, 2 mass parts of epoxidised soybean oil as stabilizer, 3 mass parts of polyethylene wax as lubricant, into
Row is kneaded, and has modulated compound A.Into compound A, the cumyl peroxide as peroxide is added so that it is opposite
Become 0.1 mass parts in 100 mass parts of haloflex, is kneaded.Thereafter, the piece mixture obtained by mixing formed
Material is granulated into the shape of 5mm square, obtains pellet.Then, the pellet is adhered each other in order to prevent, and full talcum is applied on pellet.
It is explained, when peroxide is kneaded, is well-dispersed in peroxide in haloflex and peroxide
Do not occur to carry out under the conditions of thermal decomposition is such.Specifically, the surface temperature of roller is set as 100 DEG C, in addition peroxide
It is kneaded 5 minutes later.
[grafting process]
Then, it using single axle extruding machine 100 shown in Fig. 3, is impregnated in silane compound and is obtained in addition process
Pellet, carry out grafting process.Specifically, making the 3- methacryloxypropyl trimethoxy silicon as silane compound
Alkane is impregnated in the grain obtained in addition process in the way of becoming 3.35 mass parts relative to 100 mass parts of haloflex
Material.Out of the hopper 101 of single axle extruding machine 100 investment to machine barrel 103a, screw rod will be utilized containing the pellet for being soaked with silane compound
102 rotation is transported to machine barrel 103b from machine barrel 103a.
At this point, softening mixing is carried out by heating pellet in machine barrel 103a, 103b, so that silane compound is grafted
It is copolymerized in haloflex.Silane Grafted haloflex is formed as a result,.Thereafter, Silane Grafted haloflex is transported to
The head 104 of extruder 100 squeezes out the strands 20 (length 150cm) of Silane Grafted haloflex from mouth mold 105.Then, will
Strands 20, which are directed into sink 106, carries out water cooling, removes moisture removal using air wiper (air wiper) 107.Thereafter, it utilizes
Strands 20 are granulated by pelletizer 108, obtain the pellet 21 containing Silane Grafted haloflex.
It is explained, in grafting process, uses the single axle extruding machine 100 of 40mm single shaft.In addition, by screw diameter
The ratio L/D of D and spiro rod length L is set as 25.In addition, the temperature of machine barrel 103a is set as 80 DEG C, the temperature of machine barrel 103b is set
It is 200 DEG C, the temperature on head 104 is set as 200 DEG C.
In addition, the revolving speed of screw rod 102 is set as 20rpm, screw rod 102 is made for full thread shape.In addition, as mouth mold
105, use the mouth mold that bore dia is 5mm, hole number is 3.
[the addition process of filler]
Then, to by being grafted in the pellet 21 that process obtains, various fillers is added, are carried out using 8 inch roller machines
It is kneaded.Specifically, addition various additives are so that cycloalkanes relative to 100 mass parts of haloflex, as plasticizer
It is that processing oil becomes 10 mass parts, sulfur antioxidant becomes 0.08 mass parts, amine antioxidant becomes 1.5 mass parts, makees
Become 40 mass parts as 3 mass parts, as the FEF carbon black of carbon black, as the ethylene of lubricant for the antimony trioxide of fire retardant
Double oleamides become 1 mass parts.After mixing, the sheet material formed by mixture is granulated into the shape of 5mm square, is obtained compound
The pellet of object B.It is explained, when mixing, the surface temperature of roller is set as 100 DEG C, addition is stuffed entirely with being kneaded 5 after agent
Minute.
In addition, in addition having modulated the silanol condensation catalyst comprising silanol condensation catalyst in addition to the pellet of compound B
Masterbatch.Specifically, 111 mass parts relative to compound A, add two neodecanoic acids two as silanol condensation catalyst
1 mass parts of tin octylate are kneaded using 8 inch roller machines.At this point, the surface temperature of roller is set as 100 DEG C, silanol is added
It is kneaded 3 minutes after condensation catalyst.Thereafter, the sheet material formed by mixture is granulated into the shape of 5mm square, modulates silanol
Condensation catalyst masterbatch.
Finally, adding silanol condensation catalyst masterbatch so that it is relative to compound B's into the pellet of compound B
100 mass parts of haloflex become 2.5 mass parts, and the chlorinated polyethylene composition for modulating embodiment 1 is blended by dry type.
The modulation condition of embodiment 1 is shown in following table 1.
Table 1
(embodiment 2)
In example 2, as shown in table 1, the type of silane compound is changed to 3- methacryloxypropyl three
Its additive amount is set as 3.92 mass parts relative to 100 mass parts of haloflex, in addition to this, with implementation by Ethoxysilane
Example 1 has similarly modulated chlorinated polyethylene composition.
(embodiment 3,4)
In embodiment 3,4, as shown in table 1, increase the additive amount of peroxide, changes silane compound and by peroxide
The ratio (x/2 α y) for the free radical that compound generates, in addition to this, has modulated chlorinated polyethylene composition similarly to Example 1.
In embodiment 3, the additive amount of peroxide is set as 0.5 mass parts, ratio is set as 3.7.In example 4, by peroxide
The additive amount of compound is set as 1.0 mass parts, and ratio is set as 1.8.
(comparative example 1)
In comparative example 1, as shown in table 1, peroxide and silane compound is made to be impregnated in the pellet of compound A simultaneously,
In addition to this, chlorinated polyethylene composition has been modulated similarly to Example 1.
(comparative example 2~4)
In comparative example 2~4, as shown in table 1, the content of peroxide is changed, in addition to this, similarly to Example 1
Chlorinated polyethylene composition has been modulated on ground.For the content of peroxide, it is set as 0.02 mass parts in comparative example 2, is comparing
It is set as 0.08 mass parts in example 3,1.5 mass parts are set as in comparative example 4.
(2) production of cable
Then, using single axle extruding machine 100 shown in Fig. 4, modulated chlorinated polyethylene composition is squeezed out to make
Make cable 1.Specifically, by making the sectional area 8mm as conductor 102Copper conductor be inserted through single axle extruding machine 100
Mouth mold 105 squeezes out ethylene propylene rubber (EP rubber) on their outer circumference and forms the insulating layer 11 of thickness 1.0mm, and exhausted
Above-mentioned chlorinated polyethylene composition is squeezed out on the periphery of edge layer 11 and forms the sheath 12 of thickness 1.7mm, to make cable 1.
Thereafter, cable 1 is taken care of 24 hours in the stainless steel closed container under the saturated vapor atmosphere in 60 DEG C, makes sheath
12 are crosslinked.
It is explained, in the production of cable 1, uses the single axle extruding machine 100 of 20mm single shaft.In addition, by screw rod
The ratio L/D of diameter D and spiro rod length L is set as 15.In addition, the temperature of machine barrel 103a is set as 120 DEG C, by the temperature of machine barrel 103b
Degree is set as 150 DEG C, and the temperature of cross head 110 is set as 150 DEG C, the temperature of neck 109 is set as 150 DEG C, by mouth mold 105
Temperature is set as 150 DEG C.In addition, the revolving speed of screw rod 102 is set as 15rpm, the shape of screw rod 102 is set as full thread shape.
(3) evaluation method
For chlorinated polyethylene composition, to the gel fraction after grafting process and the gel fraction after crosslinking Treatment into
Row evaluation.In addition, evaluating the appearance of cable 1.It is specifically described below.
(gel fraction)
In the present embodiment, in order to evaluate the gel fraction after grafting process, the line of Silane Grafted haloflex is used
Material 20 is used as sample.Sample 0.5g is taken from the strands 20, which is put into the brass metal mesh in 40 mesh.Then,
Extraction processing is carried out in 110 DEG C of oil bath to sample using dimethylbenzene.After extraction processing, the examination of remaining is taken out from dimethylbenzene
Sample is dried in vacuo 4 hours at 80 DEG C.Then, weigh remaining sample drying after quality, according to the examination before xylene extraction
The sample mass b of sample quality a and the remaining after xylene extraction pass through the gel fraction R that following formula calculates sample.
R (%)=b/a × 100
It is and above-mentioned in addition, take sample 0.5g from the sheath 12 of cable 1 to evaluate the gel fraction after crosslinking Treatment
Similarly calculate gel fraction.In the present embodiment, the situation that the gel fraction after crosslinking Treatment is 60% or more is set as closing
Lattice (zero), by gel fraction less than 60% the case where, are set as unqualified (×).
(appearance)
About the evaluation of appearance, evaluated according to appearance of the visual, feel to the sheath 12 of cable 1, it will be sufficiently smooth
The case where be set as qualified (zero), bad order will be led to because of rough, convex grain (protrusion of locality) etc. in sheath 12
Situation is set as unqualified (×).
(overall merit)
In the present embodiment, the qualified situation of the evaluation of gel fraction and appearance these two aspects is set as qualified (zero),
The underproof situation of in office 1 evaluation is set as unqualified (×).
(4) evaluation result
It confirmed in embodiment 1, as shown in table 1, the gel fraction of the strands after being grafted process is 2%, in grafting work
There is no the cross-linking reaction being exceedingly not intended in sequence.In addition confirmed, it is solidifying after crosslinking in the sheath 12 of embodiment 1
The height that glue score is 67% has the sufficient degree of cross linking.In addition confirmed, the appearance of sheath 12 is smooth, well.It is explained
It is, in embodiment 1, due to having used the methylacryloyl that volatility is few and penetrating odor is few compared with vinyl silanes
Silane, because reducing such problems without confirming the operating environment when modulating chlorinated polyethylene composition.
Confirmed in example 2, as shown in table 1, even if change methacryl base silane type, also with embodiment
1 similarly, and being evaluated as gel fraction and appearance is good.
It confirmed in embodiment 3,4, as shown in table 1, more increase the additive amount of peroxide and reduce ratio (x/2 α
Y), then it more can be improved the gel fraction after crosslinking.It is explained, confirmed in embodiment 3,4, due to reducing ratio
(x/2 α y) and increase the ratio of free radical, thus be grafted process after gel fraction get higher compared with Example 1.
It confirmed in comparative example 1, due to being added to methacryl base silane and peroxide simultaneously, thus after crosslinking
Gel fraction become 58%.It is believed that this is because due to simultaneously be added to methacryl base silane and peroxide, because
And consumed by the free radical that peroxide generates by methacryl base silane, it can not be by methacryl base silane effectively
Graft copolymerization.
It confirmed in comparative example 2,3, since the additive amount of peroxide is very few relative to methacryl base silane, because
And the gel fraction after being crosslinked is respectively 30%, 34%, can not obtain the sufficient degree of cross linking.It is explained, in comparative example
2, confirmed in 3, since the additive amount of peroxide is few, thus being grafted the gel fraction after process is 0%, in grafting process
The cross-linking reaction not being not intended to.
It confirmed in comparative example 4, since the additive amount of peroxide is excessive relative to methacryl base silane, thus
It will do it cross-linking reaction when being grafted process, the height that the gel fraction after being grafted process is 71%.In addition confirmed, due to grafting
The height that gel fraction after process is 71%, thus when squeezing out and forming strands Silane Grafted haloflex, spray volume
Unstable, the cutting of strands takes place frequently.In addition, being confirmed not on the surface of the sheath formed by the chlorinated polyethylene composition
Smooth situation and it is regarded as the convex grain (protrusion) generated by the excessive cross-linking reaction of locality.It is explained
It is that confirmed in comparative example 4, it is the high degree of cross linking that the gel fraction after crosslinking, which is 89%,.
It is explained, in the present embodiment, has to using by H2C=C (CH3)-CO- indicate methacryl
The case where silane compound of base, is illustrated, but it is believed that, even having by H2The acryloyl that C=CH-CO- is indicated
The silane compound of base can also obtain same effect.
The abstract > of < embodiments of the present invention
In following [1]~[5], summarize embodiments of the present invention.
[1] a kind of Silane Grafted haloflex, will have using peroxide by H2C=C (CH3)-CO- expression
The silane compound graft copolymerization of methylacryloyl is formed in haloflex, and the molal quantity of aforementioned silane compounds is set as
X, when being set as y by the molal quantity of aforementioned peroxide, the quantity of oxygen contained in aforementioned peroxide and the key of oxygen be set as α,
X/2 α y is 1.5 or more 20.0 hereinafter, the gel fraction after crosslinking is 60% or more.
[2] the Silane Grafted haloflex of [1], wherein aforementioned silane compounds include 3- methacryloxy third
Base trimethoxy silane or 3- methacryloxypropyl.
[3] a kind of manufacturing method of Silane Grafted haloflex has peroxide making an addition to haloflex
Addition process and by into aforementioned haloflex add have by H2C=C (CH3)-CO- indicate methacryl
The silane compound of base, thus by aforementioned silane compounds graft copolymerization in the grafting process of aforementioned haloflex,
In foregoing graft process, the molal quantity of aforementioned silane compounds is set as x, by the molal quantity of aforementioned peroxide
When being set as y, the quantity of oxygen contained in aforementioned peroxide and the key of oxygen being set as α, become 1.5 or more 20.0 according to x/2 α y
Mode below adds aforementioned silane compounds, and foregoing graft process is carried out after by aforementioned addition process.
[4] a kind of insulated electric conductor, the insulating layer for having conductor, being arranged in a manner of the periphery for surrounding aforementioned conductor should
Insulating layer is formed by Silane Grafted haloflex, which is will have using peroxide by H2C
=C (CH3) the silane compound graft copolymerization of methylacryloyl that indicates of-CO- forms in haloflex, by aforementioned silane
The molal quantity of compound is set as x, the molal quantity of aforementioned peroxide is set as to y, by oxygen contained in aforementioned peroxide and oxygen
The quantity of key when being set as α, x/2 α y is 1.5 or more 20.0 hereinafter, the gel fraction of the insulating layer is 60% or more.
[5] a kind of cable has conductor, the insulating layer being arranged in a manner of the periphery for surrounding aforementioned conductor, to surround
The surrounding layer that the mode of the periphery of aforementioned dielectric layer is arranged, the surrounding layer are formed by Silane Grafted haloflex, which connects
Branch haloflex is that will have using peroxide by H2C=C (CH3)-CO- indicate methylacryloyl silane chemical combination
Graft copolymers are formed in haloflex, and the molal quantity of aforementioned silane compounds is set as x, by mole of aforementioned peroxide
Number is when being set as y, the quantity of oxygen contained in aforementioned peroxide and the key of oxygen being set as α, x/2 α y be 1.5 or more 20.0 hereinafter,
The gel fraction of the cable is 60% or more.
Industrial availability
It present invention can be suitably applied to the insulated electric conductor and cable using Silane Grafted haloflex.
Symbol description
1 cable
2 insulated electric conductors
10 conductors
11 insulating layers
12 sheaths
Claims (5)
1. a kind of for electric wire or the crosslinked with silicane haloflex of cable, by comprising haloflex, there is metering system
The silane compound of acyl group and the crosslinked with silicane haloflex of peroxide are formed,
The crosslinked with silicane haloflex is made by the method with following processes:
After peroxide is made an addition to haloflex, there is methylacryloyl by adding into the haloflex
Silane compound, to obtain Silane Grafted chlorination and gather the silane compound graft copolymerization in the haloflex
Then ethylene is crosslinked the Silane Grafted haloflex,
The molal quantity of the silane compound is set as x, the molal quantity of the peroxide is set as to y, by the peroxide
Contained in the quantity of key of oxygen and oxygen when being set as α, x/2 α y be 1.5 or more 9 hereinafter,
Gel fraction after the crosslinking of the crosslinked with silicane haloflex is 60% or more.
2. the crosslinked with silicane haloflex according to claim 1 for being used for electric wire or cable, wherein
The silane compound includes 3- methacryloxypropyl trimethoxy silane or 3- methacryloxypropyl
Triethoxysilane.
3. a kind of manufacturing method for electric wire or the crosslinked with silicane haloflex of cable, includes
Peroxide is made an addition to the addition process of haloflex,
By adding the silane compound with methylacryloyl into the haloflex, thus by the silane chemical combination
Graft copolymers in the grafting process of the haloflex, and
The Silane Grafted haloflex obtained in the grafting process is crosslinked, so that the crosslinked with silicane chlorine after crosslinking
Change the cross-linking process step that the gel fraction of polyethylene is 60% or more；
In the grafting process, the molal quantity of the silane compound is being set as x, is setting the molal quantity of the peroxide
For y, the quantity of oxygen contained in the peroxide and the key of oxygen is set as α when, become 1.5 or more 9 below according to x/2 α y
Mode adds the silane compound,
The grafting process is carried out after by the addition process.
4. a kind of insulated electric conductor, it includes conductor and the periphery to surround the conductor in a manner of the insulating layer that is arranged,
The insulating layer is formed by crosslinked with silicane haloflex, which includes haloflex, has
The silane compound and peroxide of methylacryloyl,
The crosslinked with silicane haloflex is made by the method with following processes:
After peroxide is made an addition to haloflex, there is methylacryloyl by adding into the haloflex
Silane compound, to obtain Silane Grafted chlorination and gather the silane compound graft copolymerization in the haloflex
Then ethylene is crosslinked the Silane Grafted haloflex,
The molal quantity of the silane compound is set as x, the molal quantity of the peroxide is set as to y, by the peroxidating
When the quantity of the key of oxygen and oxygen contained in object is set as α, x/2 α y be 1.5 or more 9 hereinafter,
Gel fraction after the crosslinking of the insulating layer is 60% or more.
5. a kind of cable, it includes conductor, the insulating layer being arranged in a manner of the periphery for surrounding the conductor and to surround
The surrounding layer that the mode of the periphery of insulating layer is arranged is stated,
The surrounding layer is formed by crosslinked with silicane haloflex, which includes haloflex, has
The silane compound and peroxide of methylacryloyl,
The crosslinked with silicane haloflex is made by the method with following processes:
After peroxide is made an addition to haloflex, there is methylacryloyl by adding into the haloflex
Silane compound, to obtain Silane Grafted chlorination and gather the silane compound graft copolymerization in the haloflex
Then ethylene is crosslinked the Silane Grafted haloflex,
The molal quantity of the silane compound is set as x, the molal quantity of the peroxide is set as to y, by the peroxidating
When the quantity of the key of oxygen and oxygen contained in object is set as α, x/2 α y be 1.5 or more 9 hereinafter,
Gel fraction after the crosslinking of the surrounding layer is 60% or more.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014078079A JP6187368B2 (en) | 2014-04-04 | 2014-04-04 | Method for producing silane-grafted chlorinated polyethylene, method for producing insulated wire, and method for producing cable |
| JP2014-078079 | 2014-04-04 | ||
| PCT/JP2015/059429 WO2015152005A1 (en) | 2014-04-04 | 2015-03-26 | Silane-grafted chlorinated polyethylene, method for producing same, and insulated wire and cable using said polyethylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106232647A CN106232647A (en) | 2016-12-14 |
| CN106232647B true CN106232647B (en) | 2019-08-09 |
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| CN201580022355.3A Active CN106232647B (en) | 2014-04-04 | 2015-03-26 | Silane Grafted haloflex, its manufacturing method and the insulated electric conductor and cable that have used the polyethylene |
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| Country | Link |
|---|---|
| JP (1) | JP6187368B2 (en) |
| CN (1) | CN106232647B (en) |
| WO (1) | WO2015152005A1 (en) |
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| JP2017141386A (en) * | 2016-02-12 | 2017-08-17 | 古河電気工業株式会社 | Heat-resistant silane crosslinked resin molded body and method for producing the same, and silane masterbatch and heat-resistant product |
| JP6720565B2 (en) * | 2016-02-17 | 2020-07-08 | 日立金属株式会社 | Insulated wire and cable |
| JP6720711B2 (en) * | 2016-06-14 | 2020-07-08 | 日立金属株式会社 | cable |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365377A (en) * | 1999-07-30 | 2002-08-21 | Nok株式会社 | Molding material for carbon dioxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3802913A (en) * | 1970-10-28 | 1974-04-09 | Gen Electric | Pressureless curing system for chemically cross-linking ethylene containing polymers,and product formed thereby |
| JPS61101509A (en) * | 1984-10-24 | 1986-05-20 | Sunstar Giken Kk | Modified chlorinated polyolefin |
| JPH09302043A (en) * | 1996-05-16 | 1997-11-25 | Sekisui Chem Co Ltd | Production of silane-modified polyolefin |
| JP5907079B2 (en) * | 2013-01-17 | 2016-04-20 | 日立金属株式会社 | Electric wires and cables using silane-grafted chlorinated polyethylene |
-
2014
- 2014-04-04 JP JP2014078079A patent/JP6187368B2/en active Active
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- 2015-03-26 CN CN201580022355.3A patent/CN106232647B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1365377A (en) * | 1999-07-30 | 2002-08-21 | Nok株式会社 | Molding material for carbon dioxide |
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| JP6187368B2 (en) | 2017-08-30 |
| JP2015199795A (en) | 2015-11-12 |
| WO2015152005A1 (en) | 2015-10-08 |
| CN106232647A (en) | 2016-12-14 |
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