CN106232647A - Silane Grafted chlorinated polyethylene, its manufacture method and employ insulated electric conductor and the cable of this polyethylene - Google Patents
Silane Grafted chlorinated polyethylene, its manufacture method and employ insulated electric conductor and the cable of this polyethylene Download PDFInfo
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- CN106232647A CN106232647A CN201580022355.3A CN201580022355A CN106232647A CN 106232647 A CN106232647 A CN 106232647A CN 201580022355 A CN201580022355 A CN 201580022355A CN 106232647 A CN106232647 A CN 106232647A
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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
- 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 chlorinated polyethylene, its manufacture method, the insulated electric conductor employing this polyethylene and cable, described Silane Grafted chlorinated polyethylene to have the high degree of cross linking, by methylacryloyl Silane Grafted copolymerization being obtained.The present invention provides a kind of Silane Grafted chlorinated polyethylene, and it utilizes peroxide will have by H2C=C (CH3) the silane compound graft copolymerization of methylacryloyl that represents of CO forms in chlorinated polyethylene; the molal quantity of silane compound is set to x, the molal quantity of peroxide is set to y, time the quantity of oxygen contained in peroxide with the key of oxygen is set to α; x/2 α y is less than more than 1.5 20.0, and the gel fraction after crosslinking is more than 60%.
Description
Technical field
The present invention relates to Silane Grafted chlorinated polyethylene, its manufacture method and employ the insulated electric conductor of this polyethylene
And cable.
Background technology
Chlorinated polyethylene be by utilize the methods such as aqueous suspension method make the polyethylene as raw material and chlorine have an effect from
And the one in the thermoplastic elastomer (TPE) obtained.Chlorinated polyethylene has pliability, weatherability, oil resistivity, chemical resistance, fire-retardant
Property, the characteristic widely such as thermostability, abrasion performance, be widely used as being formed the surrounding layer etc. (hereinafter also referred to as sheath) of cable
Material.
Known generally in the case of being formed sheath by chlorinated polyethylene, after being extruded by chlorinated polyethylene, make chlorinated polyethylene
Alkene cross-links.As cross-linking method, the most extensively carry out using the crosslinked with silicane of silane compound (silane coupler) (such as
With reference to patent documentation 1).
In crosslinked with silicane, first, by containing silane compound and peroxide in chlorinated polyethylene, thus in mistake
By silane compound graft copolymerization in chlorinated polyethylene in the presence of oxide, form Silane Grafted chlorinated polyethylene.Then, logical
Cross and make Silane Grafted chlorinated polyethylene contact with water and cross-link, thus form crosslinked with silicane chlorinated polyethylene.
As silane compound, the most extensively apply such as vinyltrimethoxy silane, VTES
Etc. the silane compound (hereinafter also referred to as vinyl silanes) with vinyl.But, the volatility of vinyl silanes high and
There is distinctive penetrating odor, thus there is the most disposable such problem.Accordingly, as the silane replacing vinyl silanes
Compound, people are studying the silane compound with methylacryloyl, acryloyl group or styryl.Wherein, by
In becoming practicality on present aspect etc. high, thus there is the silane compound of methylacryloyl (hereinafter also referred to as metering system
Acyl silanes) receive publicity.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent clear 50-35540 publication
Summary of the invention
The problem solved is wanted in invention
Methacryl base silane and vinyl silanes are comparatively speaking difficult to graft copolymerization in chlorinated polyethylene.Therefore,
Silane Grafted chlorinated polyethylene methylacryloyl Silane Grafted copolymerization obtained there are that degree of cross linking step-down is such asks
Topic.
It is an object of the invention to provide a kind of Silane Grafted chlorinated polyethylene, its manufacture method, employ this polyethylene
Insulated electric conductor and cable, described Silane Grafted chlorinated polyethylene has the high degree of cross linking, by by methacryl base silane
Graft copolymerization and obtain.
For solving the scheme of problem
An embodiment of the invention provides a kind of Silane Grafted chlorinated polyethylene, wherein, utilizes peroxide to have
Have by H2C=C (CH3) the silane compound graft copolymerization of methylacryloyl that represents of-CO-forms in chlorinated polyethylene, by front
State the molal quantity of silane compound to be set to x, the molal quantity of aforementioned peroxide is set to y, by contained in aforementioned peroxide
When the quantity of the key of oxygen and oxygen is set to α, x/2 α y is less than more than 1.5 20.0, the gel fraction (gel after crosslinking
Fraction) it is more than 60%.
Other embodiments of the present invention provide the manufacture method of a kind of Silane Grafted chlorinated polyethylene, and it has: incited somebody to action
Oxide makes an addition to the interpolation operation of chlorinated polyethylene, and has by H by adding in aforementioned chlorinated polyethylene2C=C
(CH3) silane compound of methylacryloyl that represents of-CO-, thus by aforementioned silane compounds graft copolymerization in aforementioned chlorine
Change the grafting operation of polyethylene；In foregoing graft operation, the molal quantity of aforementioned silane compounds is set to x, by aforementioned peroxide
The molal quantity of compound is set to y, time the quantity of oxygen contained in aforementioned peroxide with the key of oxygen is set to α, become according to x/2 α y
The mode of less than more than 1.5 20.0 adds aforementioned silane compounds, is carrying out foregoing graft work after aforementioned interpolation operation
Sequence.
Other embodiments of the present invention provide a kind of insulated electric conductor, and it comprises conductor, to surround the periphery of aforementioned conductor
The insulating barrier that arranges of mode, this insulating barrier is formed by Silane Grafted chlorinated polyethylene, and this Silane Grafted chlorinated polyethylene is profit
To have by H with peroxide2C=C (CH3) the silane compound graft copolymerization of methylacryloyl that represents of-CO-is in chlorination
Polyethylene forms, and the molal quantity of aforementioned silane compounds is set to x, the molal quantity of aforementioned peroxide is set to y, by aforementioned mistake
When the quantity of oxygen contained in oxide and the key of oxygen is set to α, x/2 α y is less than more than 1.5 20.0, gel fraction be 60% with
On.
Other embodiments of the present invention provide a kind of cable, and it comprises conductor, to surround the side of the periphery of aforementioned conductor
The insulating barrier that formula is arranged, the surrounding layer that arranges in the way of surrounding the periphery of aforementioned dielectric layer, this surrounding layer is by Silane Grafted chlorine
Changing polyethylene to be formed, this Silane Grafted chlorinated polyethylene is to utilize peroxide will have by H2C=C (CH3) first that represents of-CO-
The silane compound graft copolymerization of base acryloyl group forms in chlorinated polyethylene, the molal quantity of aforementioned silane compounds is set to x,
The molal quantity of aforementioned peroxide is set to y, time the quantity of oxygen contained in aforementioned peroxide with the key of oxygen is set to α, x/2
α y is less than more than 1.5 20.0, and gel fraction is more than 60%.
The effect of invention
According to an embodiment of the invention, it is provided that a kind of have the high degree of cross linking and connect by methacryl base silane
Branch copolymerization and the Silane Grafted chlorinated polyethylene, its manufacture method, the insulated electric conductor employing this polyethylene and the cable that obtain.
Accompanying drawing explanation
Fig. 1 is the sectional view of the cable involved by an embodiment of the invention.
Fig. 2 is the sectional view of the insulated electric conductor involved by an embodiment of the invention.
Fig. 3 is the explanatory diagram representing the grafting operation employing extruder in the embodiment of the present invention.
Fig. 4 is the explanatory diagram of the manufacturing process representing the cable in the embodiment of the present invention.
Detailed description of the invention
Above-mentioned problem is studied by the present inventor etc., it was found that methacryl base silane and vinyl silanes phase
Comparatively speaking graft copolymerization it is difficult to low in grafting rate on chlorinated polyethylene of chlorinated polyethylene, i.e. methacryl base silane
Reason be that methacryl base silane easily reacts with the free radical of generation when graft copolymerization.For this point, with
Under be specifically described.
It is said that in general, the graft copolymerization of silane compound is carried out by free radical.Specifically, first, by making chlorine
Change in polyethylene containing silane compound and peroxide and heat, carrying out thermally decomposing by peroxide thus generate freedom
Base (such as oxygen-derived free radicals).Oxygen-derived free radicals is by the hydrogen captured in chlorinated polyethylene thus the free radical generating chlorinated polyethylene.
Then, the unsaturated bond (such as vinyl, methylacryloyl) that the free radical of chlorinated polyethylene and silane compound are had
React, thus silane compound by graft copolymerization in chlorinated polyethylene.So, the graft copolymerization of silane compound by by
Peroxide generate oxygen-derived free radicals and start reaction.
But, in above-mentioned graft copolymerization, the oxygen-derived free radicals of original and chlorinated polyethylene alkene reaction sometimes with silanization
Compound reacts.That is, oxygen-derived free radicals is consumed because reacting with silane compound sometimes.Therefore, oxygen-derived free radicals and chlorination
The reaction of polyethylene is hindered, so that the free radical of chlorinated polyethylene is not likely to produce.As a result of which it is, silane compound is not
Can fully graft copolymerization in chlorinated polyethylene so that the grafting rate step-down of silane compound.Particularly, at silane compound
In, methacryl base silane due to vinyl silanes etc. comparatively speaking with the reactive high of oxygen-derived free radicals and easily with
Oxygen-derived free radicals reacts, thus grafting rate can be lower.If so the grafting rate step-down of silane compound, then make silane
When graft CPE cross-links, the degree of cross linking can step-down.
The method solving this problem is studied by the present inventor etc., it was found that preferably added by peroxide
After chlorinated polyethylene, add methacryl base silane rather than methacryl base silane is added with peroxide simultaneously
Add.In the past, when peroxide and silane compound are made an addition to chlorinated polyethylene, such as, make peroxide and silane by interpolation
Compound dissolution and the solution that obtains, thus they are added simultaneously.But, in the case of methacryl base silane, if
Add with peroxide simultaneously, then during making them be scattered in chlorinated polyethylene, peroxide generate
Free radical and methylacryloyl silane reaction, thus peroxide is consumed, result causes connecing of methacryl base silane
Branch copolymerization is hindered.On the other hand, in the case of adding methacryl base silane after with the addition of peroxide, due to
In advance peroxide can be scattered in chlorinated polyethylene, thus suppress peroxide when enabling methacryl base silane to disperse
The consumption of compound.As a result of which it is, can on chlorinated polyethylene graft copolymerization methacryl base silane well.Base of the present invention
Complete in these opinions.
＜ an embodiment of the invention ＞
Hereinafter an embodiment of the invention is illustrated.
(1) Silane Grafted chlorinated polyethylene
The Silane Grafted chlorinated polyethylene of present embodiment, is to utilize peroxide will have the silane of methylacryloyl
Compound (methacryl base silane) graft copolymerization obtains in chlorinated polyethylene.Silane Grafted chlorinated polyethylene is at molecule
Chain has the silylation being derived from silane compound, has and cross-link such structure by carrying out reacting with water.Below to respectively
Composition is specifically described.
Chlorinated polyethylene, such as by by wire polyethylene (Low Density Polyethylene, high density polyethylene (HDPE) etc.) suspended dispersed
Yu Shuizhong and obtain waterborne suspension, chlorine is blown into this waterborne suspension and obtains.About the chlorination degree of chlorinated polyethylene,
From the grafting rate improving silane compound, i.e. from the viewpoint of improving degree of cross linking when making it cross-link, be preferably set to 25% with
Upper less than 45%, more preferably it is set to less than more than 30% 40%.
Silane compound has by H2C=C (CH3) methylacryloyl that represents of-CO-.Methylacryloyl is and chlorination
The free radical of polyethylene carries out the substituent group of the unsaturated bond reacted.Silane compound passes through methylacryloyl and chlorinated polyethylene
The free radical of alkene carries out reacting thus graft copolymerization is in chlorinated polyethylene.
It addition, silane compound has water-disintegrable silylation.In the chemical constitution of Silane Grafted chlorinated polyethylene, logical
Cross and silane compound graft copolymerization in chlorinated polyethylene thus is imported silylation.Silylation makes Silane Grafted chlorinated polyethylene
When reacting with water and cross-link, become silanol group by hydrolysis.Silanol group passes through dehydrating condensation (silanol condensation)
And form cross-linked structure.As silylation, include, for example the hydrolyzable knots such as there is halogen, alkoxyl, acyloxy, phenoxy group
The silylation of structure.As having the silylation of these hydrolyzable structures, include, for example halosilyl, alkoxyl first silicon
Alkyl, acyloxysilyl, phenoxy group silicyl etc..
Specifically, as silane compound, 3-methacryloxypropyl trimethoxy silane, 3-methyl can be used
Acryloxypropyl triethoxysilane, 3-methacryloyloxypropyl methyl dimethoxysilane, 3-methacryl
The methacryl base silanes such as epoxide hydroxypropyl methyl diethoxy silane.
Peroxide is for the material of graft copolymerization silane compound on chlorinated polyethylene.As peroxide, can
Use and capture the hydrogen-taking capacity height of hydrogen from chlorinated polyethylene and can be not easily deteriorated at chlorinated polyethylene (being difficult to dehydrochlorination)
Temperature carries out thermally decomposing and generating the organic peroxide of oxygen-derived free radicals.Owing to the deterioration initial temperature of chlorinated polyethylene is 200
About DEG C, thus as peroxide, it is the organic peroxy of more than 120 DEG C less than 200 DEG C that 1 minute half life temperature is preferably used
Compound.From the viewpoint of shortening graft reaction required time, more preferably using 1 minute half life temperature is more than 150 DEG C 200
Organic peroxide below DEG C.Being explained, 1 minute half life temperature refers to that the half-life of peroxide becomes 1 point
The temperature of clock.
Specifically, as peroxide, (peroxidating two is different for peroxide can to use double (1-methyl isophthalic acid-phenylethyl)
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, it is possible to and use two or more.In them, 1 minute half life temperature can be used to be about 175 DEG C double
(1-methyl isophthalic acid-phenylethyl) peroxide (so-called cumyl peroxide).
About silane compound and peroxide, the molal quantity of silane compound is set to x, by peroxide mole
Number is set to y, time the quantity of oxygen contained in peroxide with the key (peroxide bridge ,-O-O-key) of oxygen is set to α, x/2 α y is preferably
Less than more than 1.5 20.0, more preferably less than more than 39.X/2 α y represents the silane compound that is matched with in chlorinated polyethylene
The ratio of molal quantity and the molal quantity of the free radical (oxygen-derived free radicals) generated by peroxide.If x/2 α y is less than 1.5, then due to
There is the tendency that free radical is not enough for silane compound, thus likely silane compound cannot be grafted fully
Copolymerization is in chlorinated polyethylene.On the other hand, if x/2 α y is more than 20.0, then owing to there is free radical relative to silane compound
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 to be set to less than more than 1.5 20, then can make the abundant graft copolymerization of silane compound in chlorinated polyethylene, and
Can suppress to make cross-linking reaction during its graft copolymerization.
For silane compound and peroxide, if x/2 α y becomes less than more than 1.5 20.0 such content then
It is not particularly limited.Such as, relative to chlorinated polyethylene 100 mass parts, the content of silane compound be preferably 1.0 mass parts with
Below upper 10 mass parts.The content of peroxide is preferably below more than 0.03 mass parts 3.0 mass parts.Now, silane chemical combination
The molal quantity x of thing is preferably 4.0 × 10-3～4.0 × 10-2In the range of, peroxide the free radical (oxygen-derived free radicals) generated
Molal quantity 2 α y be preferably 2.2 × 10-4～2.2 × 10-2In the range of.
In Silane Grafted chlorinated polyethylene, from the viewpoint of cross-linking from effectively making it, preferably comprise promotion crosslinking anti-
The silanol condensation catalyst answered.As silanol condensation catalyst, such as, magnesium, Gai Deng II race element, cobalt, ferrum etc. can be used
VIII element, the metallic element such as stannum, zinc and titanium, comprise the metallic compound of these elements.It addition, can use octanoic acid, oneself
The slaine of diacid, amine compound, acid etc..Specifically, two neodecanoic acid dioctyl tins, di lauric dibutyl can be used
Stannum, dibutyltin diacetate, two octanoic acid dibutyl tin, stannous acetate, stannous octoate, lead naphthenate, zinc octoate, cobalt naphthenates etc.
Slaine, the mineral acids such as amine compound, sulphuric acid, hydrochloric acid such as ethamine, dibutyl amine, hexylamine, pyridine, toluenesulfonic acid, acetic acid, tristearin
The organic acid such as acid, maleic acid.
It addition, in Silane Grafted chlorinated polyethylene, it is possible to containing plasticizer, antioxidant (comprising age resister), white carbon black
Deng filler, other the additive such as fire retardant, lubricant, copper evil variable color preventing agent, crosslinking coagent, stabilizer.
(2) crosslinked with silicane chlorinated polyethylene
Crosslinked with silicane chlorinated polyethylene by make above-mentioned Silane Grafted chlorinated polyethylene react with water thus carry out cross-linking and
Obtain.It is more than 60% about crosslinked with silicane chlorinated polyethylene, the such as gel fraction as the index of the degree of cross linking.If gel divides
Count less than 60%, then the degree of cross linking step-down of crosslinked with silicane chlorinated polyethylene, thus the surrounding layer such as possessed for cable (protects
Set), it is impossible to obtain the mechanical properties such as hot strength.From the viewpoint of the mechanical property improving sheath etc., gel fraction upper
Limit value is not particularly limited.Gel fraction more uprises, and the degree of cross linking more uprises, then formed the most in crosslinked with silicane chlorinated polyethylene
Cross-linked structure, thus the mechanical property of sheath etc. shows the tendency of rising mostly.
Gel fraction is obtained as described below.First, crosslinked with silicane chlorinated polyethylene the sample formed is immersed in two
In toluene, it is made to seethe with excitement dimethylbenzene heating.Thereafter, the sample taking out the undissolved remaining in dimethylbenzene (extracts with hot dimethylbenzene
Sample after taking), it is dried, measures by the quality of the sample after hot xylene extraction.Then, hot dimethylbenzene is used by calculating
Sample mass after extraction is relative to the ratio of the sample mass before hot xylene extraction, thus obtains crosslinked with silicane chlorination
The gel fraction of polyethylene.Sample mass before hot xylene extraction is set to a, by with the sample after hot xylene extraction
When quality is set to b, gel fraction R is expressed from the next.
R (%)=(b/a) × 100
(3) manufacture method of Silane Grafted chlorinated polyethylene
Then, the manufacture method of above-mentioned Silane Grafted chlorinated polyethylene is illustrated.
(interpolation operation)
First, in chlorinated polyethylene, add such as cumyl peroxide as peroxide, carry out adding hot milling.Logical
Cross mixing, peroxide is scattered in chlorinated polyethylene.Now, relative to chlorinated polyethylene 100 mass parts, 0.03 matter is added
Measure the peroxide of below more than part 3.0 mass parts, preferably add the peroxide of below more than 0.1 mass parts 1.2 mass parts.
Being explained, temperature time mixing is preferably set to below the degradation temperatures of chlorinated polyethylene.
(grafting operation)
Then, in the chlorinated polyethylene being dispersed with peroxide, the methacryl with methylacryloyl is added
Base silane, carries out adding hot milling.By mixing, methacryl base silane is made to be scattered in chlorinated polyethylene.In grafting operation
In, the molal quantity of silane compound is set to x, the molal quantity of peroxide is set to y, by oxygen contained in peroxide and oxygen
The quantity of key when being set to α, preferably become the mode of less than more than 1.5 20.0 according to x/2 α y and add methacryl base silane.
Such as, relative to chlorinated polyethylene 100 mass parts, the methacryl of below more than 1.0 mass parts 10 mass parts is preferably added
Base silane.
By methacryl base silane is made an addition in chlorinated polyethylene, thus by methyl in the presence of peroxide
Acryl silane graft copolymerization, in chlorinated polyethylene, forms Silane Grafted chlorinated polyethylene.In the present embodiment, by inciting somebody to action
Peroxide makes an addition to chlorinated polyethylene in advance and makes it disperse, thus makes methacryl base silane be scattered in chlorinated polyethylene
During alkene, it is possible to suppress the reaction of oxygen-derived free radicals and the methacryl base silane generated by peroxide.I.e., it is possible to make by peroxide
The oxygen-derived free radicals that compound generates reacts efficiently with chlorinated polyethylene, generates the free radical of chlorinated polyethylene efficiently.Thus, i.e.
Make when using the methacryl base silane high with the reactivity of oxygen-derived free radicals, it is also possible to graft copolymerization gathers in chlorination aptly
Ethylene.
It is explained, in above-mentioned interpolation operation and grafting operation, such as by using roller machine, extruder, pinching
The mixing reaction units such as conjunction machine, mixer, autoclave carry out mixing being preferred.It addition, compounding conditions, graft reaction condition (temperature,
Time etc.) it is not particularly limited.
(4) composition of cable and manufacture method
Below, the cable 1 of an embodiment of the invention is illustrated.Fig. 1 is an embodiment of the invention
The sectional view of involved cable 1.
As it is shown in figure 1, the cable 1 of present embodiment possesses conductor 10.As conductor 10, can use by hypoxia copper, nothing
Copper cash that oxygen copper etc. are formed, copper alloy wire, the metal wire formed by aluminum, silver etc. or by the twisted line of metal wire twisted.
The external diameter of conductor 10 suitably can change according to the purposes of cable 1.
Insulating barrier 11 it is provided with in the way of the periphery of coated conductor 10.Insulating barrier 11 is by always known resin combination
Thing, such as, the resin combination comprising ethylene propylene rubber is formed.The thickness of insulating barrier 11 can be fitted according to the purposes of cable 1
Preferably change.
It is provided with surrounding layer 12 (sheath 12) in the way of by the periphery of insulating layer coating 11.Sheath 12 is by by making silane connect
The crosslinked with silicane chlorinated polyethylene that branch chlorinated polyethylene carries out cross-linking and obtains is formed.Sheath 12 is more than 60% by gel fraction
Crosslinked with silicane chlorinated polyethylene formed, there is the high degree of cross linking.
Cable 1 manufactures the most as follows.First, as conductor 10, prepare such as copper cash.And, such as, utilize extrusion
Machine, extrudes the resin combination comprising ethylene propylene rubber in the way of the periphery of coated conductor 10, thus forms predetermined thickness
Insulating barrier 11.Then, gather according to the predetermined thickness above-mentioned Silane Grafted chlorination of extrusion in the way of by the periphery of insulating layer coating 11
Ethylene, thus form sheath 12.Thereafter, by making the Silane Grafted chlorinated polyethylene of formation sheath 12 react with water, form silicon
The crosslinkable chlorinated polyethylene of alkane, so that sheath 12 cross-links.Specifically, at the Silane Grafted chlorinated polyethylene forming sheath 12
In alkene, cause the silylation in chemical constitution to be hydrolyzed by reacting with water, thus become silanol group.Further, pass through
Silanol group carries out dehydrating condensation and combines, thus the strand of Silane Grafted chlorinated polyethylene cross-links, thus forms silicon
The crosslinkable chlorinated polyethylene of alkane.Thus, make sheath 12 cross-link, thus obtain the cable 1 of present embodiment.It is explained
It is when making Silane Grafted chlorinated polyethylene cross-link, such as, to be preferred under the atmosphere of the saturated vapor of 60 DEG C.
Effect ＞ of ＜ embodiments of the present invention
According to present embodiment, play one or more effects shown below.
A (), according to present embodiment, is carrying out grafting operation after the interpolation operation of peroxide.That is, by inciting somebody to action
Peroxide makes an addition to chlorinated polyethylene, thereafter add methacryl base silane so that silane compound graft copolymerization in
Chlorinated polyethylene, forms Silane Grafted chlorinated polyethylene.Carry out making methacryl base silane be scattered in chlorinated polyethylene
During graft copolymerization, owing in advance peroxide being made an addition to chlorinated polyethylene and making it disperse, it is thus possible to suppression is by peroxidating
The oxygen-derived free radicals of thing generation and the reaction of methacryl base silane.I.e., it is possible to by making oxygen-derived free radicals enter with chlorinated polyethylene
Row reaction, thus generate the free radical of chlorinated polyethylene efficiently.Thereby, it is possible to methacryl base silane is grafted aptly
Copolymerization is in chlorinated polyethylene, it is possible to increase the grafting rate of the methacryl base silane in Silane Grafted chlorinated polyethylene.Cause
This, when making Silane Grafted chlorinated polyethylene cross-link, it is possible to obtains gel fraction and is more than 60%, has the high degree of cross linking
Crosslinked with silicane chlorinated polyethylene.
On the other hand, as in the past, if methacryl base silane and peroxide are made an addition to chlorinated polyethylene simultaneously
Alkene, then when making them be scattered in chlorinated polyethylene, by the oxygen-derived free radicals and the methylacryloyl silicon that are generated by peroxide
Alkane reacts, thus peroxide is consumed.Therefore, it is impossible to make the graft copolymerization effectively of methacryl base silane in chlorination
Polyethylene.As a result of which it is, cause the grafting rate of methacryl base silane to reduce, Silane Grafted chlorinated polyethylene is made to hand over
Gel fraction during connection will be less than 60%.
B (), according to present embodiment, carries out graft copolymerization making methacryl base silane be scattered in chlorinated polyethylene
Time, in advance peroxide is made an addition to chlorinated polyethylene and makes it disperse.Therefore, it is possible to by the scattered peroxide of institute in chlorination
Polyethylene produces free radical equably.Then, by making methacryl base silane be homogeneously dispersed in chlorinated polyethylene,
It is thus possible to make the graft copolymerization equably of methacryl base silane in the chemical constitution of chlorinated polyethylene, and import equably
Silylation.Thus, owing to chlorinated polyethylene can be made to cross-link equably, it is thus possible to reduce the friendship of crosslinked with silicane chlorinated polyethylene
Connection degree deviation (locality crosslinking), and improve the mechanical properties such as percentage elongation.It addition, can reduce because of chlorinated polyethylene locality mistake
The bad order that the convex grain (Star Block) that degree carries out cross-linking and generates etc. are caused.
(c) according to present embodiment, the molal quantity of silane compound is set to x, the molal quantity of peroxide is set to y,
When the quantity of oxygen contained in peroxide with the key of oxygen is set to α, x/2 α y is less than more than 1.5 20.0.If x/2 α y is 1.5
Above, then by enough and fully supplying free radical relative to methacryl base silane such that it is able to make methacryl
Base silane graft copolymerization effectively is in chlorinated polyethylene.If x/2 α y is less than 20.0, then by relative to methylacryloyl silicon
Alkane supplies free radical according to superfluous mode, thus when making methylacryloyl Silane Grafted copolymerization, it is possible to suppression chlorination
Polyethylene carries out cross-linking reaction.Therefore, if x/2 α y is set to less than more than 1.5 20, then silane compound can be made to connect fully
Branch copolymerization is in chlorinated polyethylene, and cross-linking reaction when can suppress to carry out graft copolymerization.
D (), according to present embodiment, substitutes volatility height by use methacryl base silane and has zest
The vinyl silanes of abnormal smells from the patient such that it is able to improve working environment, and can stably carry out being grafted operation.It addition, methyl
Acryl silane is boiling point, flash-point height compared with vinyl silanes, thus can suppress to send out in the manufacturing processes such as grafting operation
Light a fire calamity.
E () forms, by coagulating by making Silane Grafted chlorinated polyethylene carry out crosslinking according to present embodiment, the sheath of cable
Glue mark is the crosslinked with silicane chlorinated polyethylene formation of more than 60%.Therefore, cable has high mechanical strength.
＜ other embodiments of the present invention ＞
Above, specifically illustrate an embodiment of the invention, but the present invention is not only restricted to above-mentioned embodiment, can
Suitably changing without departing from the range of its main idea.
In above-mentioned embodiment, to using Silane Grafted chlorinated polyethylene in the surrounding layer 12 (sheath 12) of cable 1
Situation be illustrated, but be not limited to this.For example, it is also possible to make in the insulating barrier 11 of insulated electric conductor 2 as shown in Figure 2
Use Silane Grafted chlorinated polyethylene.In the case, in time utilizing above-mentioned embodiment and form sheath 12 in the same manner as, leading
The periphery of body 10 is extruded Silane Grafted chlorinated polyethylene and is formed insulating barrier 11, makes insulating barrier 11 contact with water and carry out crosslinkable silane
Connection is preferred.
Embodiment
Below, embodiments of the invention are described.
The material used in embodiment and comparative example is as follows.
Chlorinated polyethylene (Mooney viscosity (ML1+4) when 121 DEG C: 55, heat of fusion: less than 1.0J/g): Hangzhou section profit
Chemical Co., Ltd's system " CM352L "
Brucite: Kyowa Chemical Industry Co., Ltd's system " Magcellar (マ グ セ ラ) 1 "
Epoxidised soybean oil: NOF Corp's system " Newcizer 510R "
Tissuemat E (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 system antioxidant (4,4 '-thiobis (3 methy 6 tert butyl phenol)): imperial palace emerging chemical industry strain formula
Commercial firm's system " Nocrac 300R "
Amine system antioxidant (2,2,4 trimethyl 1,2 dihydroquinoline polymer): imperial palace emerging chemical industry strain formula
Commercial firm's system " Nocrac 224 "
Fire retardant (antimony trioxide): Sumitomo Metal Mining Co., Ltd's system " antimony trioxide "
Carbon (FEF white carbon black): Asahi Carbon Co., Ltd.'s system " Asahi Carbon 60G "
Lubricant (the double oleamide 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, carry out the interpolation operation of peroxide, grafting operation and the interpolation operation of filler successively,
Thus modulated the chlorinated polyethylene composition containing Silane Grafted chlorinated polyethylene.
[the interpolation operation of peroxide]
First, use 8 inch roller machines, relative to chlorinated polyethylene 100 mass parts of powder, add as stabilizer
Brucite 6 mass parts, epoxidised soybean oil 2 mass parts as stabilizer, Tissuemat E 3 mass parts as lubricant, enter
Row is mixing, has modulated complex A.In this complex A, add the cumyl peroxide as peroxide so that it is relative
Become 0.1 mass parts in chlorinated polyethylene 100 mass parts, carry out mixing.Thereafter, the sheet that will be formed by the mixing mixture obtained
Material is a granulated into the shape that 5mm is square, it is thus achieved that pellet.Then, in order to prevent this pellet from adhering each other, pellet applies full Talcum.
It is explained, by time mixing for peroxide, is well-dispersed in chlorinated polyethylene and peroxide making peroxide
Do not thermally decompose such under the conditions of carry out.Specifically, the surface temperature of roller is set to 100 DEG C, adds peroxide
The most mixing 5 minutes.
[grafting operation]
Then, use the single axle extruding machine 100 shown in Fig. 3, make silane compound be impregnated in and obtain in adding operation
Pellet, carry out be grafted operation.Specifically, the 3-methacryloxypropyl trimethoxy silicon as silane compound is made
Alkane is impregnated in the grain obtained in adding operation according to the mode becoming 3.35 mass parts relative to chlorinated polyethylene 100 mass parts
Material.By putting into machine barrel 103a from the hopper 101 of single axle extruding machine 100 containing the pellet being soaked with silane compound, utilize screw rod
The rotation of 102 is transported to machine barrel 103b from machine barrel 103a.
Now, carry out softening mixing by pellet is heated in machine barrel 103a, 103b, thus silane compound is grafted
Copolymerization is in chlorinated polyethylene.Thus, Silane Grafted chlorinated polyethylene is formed.Thereafter, Silane Grafted chlorinated polyethylene is transported to
The head 104 of extruder 100, extrudes the strands 20 (length 150cm) of Silane Grafted chlorinated polyethylene from mouth die 105.Then, will
Strands 20 is directed in tank 106 and carries out water-cooled, utilizes air wiper (air wiper) 107 to remove moisture removal.Thereafter, utilize
Strands 20 is carried out pelletize by comminutor 108, obtains the pellet 21 containing Silane Grafted chlorinated polyethylene.
It is explained, in grafting operation, uses the single axle extruding machine 100 of 40mm single shaft.It addition, by screw diameter
The ratio L/D of D and spiro rod length L is set to 25.It addition, the temperature of machine barrel 103a is set to 80 DEG C, the temperature of machine barrel 103b is set
It is 200 DEG C, the temperature of head 104 is set to 200 DEG C.
It addition, the rotating speed of screw rod 102 is set to 20rpm, screw rod 102 is made for full thread shape.It addition, as mouth die
105, use bore dia is 5mm, hole number is the mouth die of 3.
[the interpolation operation of filler]
Then, in the pellet 21 obtained by grafting operation, add various filler, use 8 inch roller machines to carry out
Mixing.Specifically, various additive is added so that relative to chlorinated polyethylene 100 mass parts, as the cycloalkanes of plasticizer
It is that processing oil becomes 10 mass parts, sulfur system antioxidant becomes 0.08 mass parts, amine system antioxidant becomes 1.5 mass parts, work
Become 3 mass parts for the antimony trioxide of fire retardant, FEF white carbon black as white carbon black becomes 40 mass parts, ethylene as lubricant
Double oleamides become 1 mass parts.After mixing, mixing thing the sheet material formed be a granulated into the square shape of 5mm, be combined
The pellet of thing B.Be explained, time mixing, the surface temperature of roller be set to 100 DEG C, add be stuffed entirely with agent after mixing 5
Minute.
It addition, except the pellet of complex B, additionally modulated the silanol condensation catalyst comprising silanol condensation catalyst
Masterbatch.Specifically, relative to 111 mass parts of complex A, two neodecanoic acids two as silanol condensation catalyst are added
Tin octylate 1 mass parts, uses 8 inch roller machines to carry out mixing.Now, the surface temperature of roller is set to 100 DEG C, adds silanol
After condensation catalyst mixing 3 minutes.Thereafter, the sheet material formed is a granulated into mixing thing the square shape of 5mm, modulates silanol
Condensation catalyst masterbatch.
Finally, in the pellet of complex B, add silanol condensation catalyst masterbatch so that it is relative to complex B's
Chlorinated polyethylene 100 mass parts becomes 2.5 mass parts, is blended by dry type and modulates the chlorinated polyethylene composition of embodiment 1.
The modulation condition of embodiment 1 is shown in table 1 below.
Table 1
(embodiment 2)
In example 2, as shown in table 1, the kind of silane compound is changed to 3-methacryloxypropyl three
Ethoxysilane, is set to 3.92 mass parts by its addition relative to chlorinated polyethylene 100 mass parts, in addition, with enforcement
Example 1 has similarly modulated chlorinated polyethylene composition.
(embodiment 3,4)
In embodiment 3,4, as shown in table 1, increase the addition of peroxide, change silane compound and by peroxide
The ratio (x/2 α y) of the free radical that compound produces, in addition, has modulated chlorinated polyethylene composition similarly to Example 1.
In embodiment 3, the addition of peroxide is set to 0.5 mass parts, ratio is set to 3.7.In example 4, by peroxide
The addition of compound is set to 1.0 mass parts, and ratio is set to 1.8.
(comparative example 1)
In comparative example 1, as shown in table 1, make peroxide and silane compound be impregnated in the pellet of complex A simultaneously,
In addition, 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, similarly to Example 1
Ground, has modulated chlorinated polyethylene composition.For the content of peroxide, comparative example 2 is set to 0.02 mass parts, is comparing
Example 3 is set to 0.08 mass parts, comparative example 4 is set to 1.5 mass parts.
(2) making of cable
Then, utilize the single axle extruding machine 100 shown in Fig. 4, extrude the chlorinated polyethylene composition modulated thus make
Make cable 1.Specifically, it is 8mm as the sectional area of conductor 10 by making2Copper conductor be inserted through single axle extruding machine 100
Mouth die 105, extrudes ethylene propylene rubber (EP rubber) on their outer circumference and forms the insulating barrier 11 of thickness 1.0mm, and absolutely
Extrude above-mentioned chlorinated polyethylene composition on the periphery of edge layer 11 and form the sheath 12 of thickness 1.7mm, thus make cable 1.
Thereafter, by keeping 24 hours in the cable 1 stainless steel hermetic container under the saturated vapor atmosphere being in 60 DEG C, sheath is made
12 cross-link.
It is explained, in the making of cable 1, uses the single axle extruding machine 100 of 20mm single shaft.It addition, by screw rod
The ratio L/D of diameter D and spiro rod length L is set to 15.It addition, the temperature of machine barrel 103a is set to 120 DEG C, by the temperature of machine barrel 103b
Degree is set to 150 DEG C, the temperature of cross head 110 is set to 150 DEG C, the temperature of cervical region 109 is set to 150 DEG C, by mouth die 105
Temperature is set to 150 DEG C.It addition, the rotating speed of screw rod 102 is set to 15rpm, the shape of screw rod 102 is set to full thread shape.
(3) evaluation methodology
For chlorinated polyethylene composition, the gel fraction after grafting operation and the gel fraction after crosslinking Treatment are entered
Row is evaluated.It addition, the outward appearance of cable 1 is evaluated.Below it is specifically described.
(gel fraction)
In the present embodiment, in order to evaluate the gel fraction after being grafted operation, the line of Silane Grafted chlorinated polyethylene is used
Material 20 is as sample.From this strands 20, take sample 0.5g, this sample is put into the pyrite wire netting in 40 mesh.Then,
Utilize dimethylbenzene that sample is carried out in the oil bath of 110 DEG C extraction process.After extraction processes, take out the examination of remaining from dimethylbenzene
Sample, is vacuum dried 4 hours at 80 DEG C.Then, the dried quality of the sample of remaining is weighed, according to the examination before xylene extraction
The sample mass b of the remaining after sample quality a and xylene extraction, calculates the gel fraction R of sample by following formula.
R (%)=b/a × 100
It addition, in order to evaluate the gel fraction after crosslinking Treatment, take sample 0.5g from the sheath 12 of cable 1, with above-mentioned
Similarly calculate gel fraction.In the present embodiment, it is set to the situation that the gel fraction after crosslinking Treatment is more than 60% close
Lattice (zero), by gel fraction less than 60% situation be set to defective (×).
(outward appearance)
About the evaluation of outward appearance, according to visual, feel, the outward appearance of the sheath 12 of cable 1 is evaluated, will be the most smooth
Situation be set to qualified (zero), in sheath 12, bad order will be caused because of grain rough, convex (projection of locality) etc.
Situation be set to defective (×).
(overall merit)
In the present embodiment, the qualified situation of evaluating of gel fraction and outward appearance these two aspects is set to qualified (zero),
The underproof situation of evaluation by office 1 be set to defective (×).
(4) evaluation result
Confirming in embodiment 1, as shown in table 1, the gel fraction of the strands after grafting operation is 2%, in grafting work
Sequence the most exceedingly carries out the cross-linking reaction being not intended to.Additionally confirm, in the sheath 12 of embodiment 1, coagulating after crosslinking
Glue mark is the height of 67%, has the sufficient degree of cross linking.Additionally confirming, the outward appearance of sheath 12 smooths, well.It is explained
It is, in embodiment 1, owing to employing the methylacryloyl that volatility compared with vinyl silanes is few and penetrating odor is few
Silane, reduces such problem hence without confirming the working environment when modulating chlorinated polyethylene composition.
Confirm in example 2, as shown in table 1, even if the kind of change methacryl base silane, also with embodiment
1 similarly, and being evaluated as of gel fraction and outward appearance is good.
Embodiment 3,4 confirms, as shown in table 1, more increases the addition of peroxide and reduce ratio (x/2 α
Y), the gel fraction after crosslinking can the most more be improved.It is explained, confirms in embodiment 3,4, owing to reducing ratio
(x/2 α y) and increase the ratio of free radical, thus grafting operation after gel fraction uprise compared with Example 1.
Comparative example 1 confirms, owing to the addition of methacryl base silane and peroxide simultaneously, thus after crosslinking
Gel fraction become 58%.It is believed that this is because, owing to the addition of methacryl base silane and peroxide simultaneously, because of
And the free radical produced by peroxide is consumed by methacryl base silane, it is impossible to by methacryl base silane effectively
Graft copolymerization.
Comparative example 2,3 confirms, owing to the addition of peroxide is very few relative to methacryl base silane, because of
And the gel fraction after cross-linking is respectively 30%, 34%, it is impossible to obtain the sufficient degree of cross linking.It is explained, at comparative example
2, confirming in 3, owing to the addition of peroxide is few, thus the gel fraction after grafting operation is 0%, in grafting operation
Do not carry out the cross-linking reaction being not intended to.
Comparative example 4 confirms, owing to the addition of peroxide is too much relative to methacryl base silane, thus
Cross-linking reaction, the height that gel fraction is 71% after grafting operation can be carried out when being grafted operation.Additionally confirm, due to grafting
Gel fraction after operation is the height of 71%, thus when Silane Grafted chlorinated polyethylene extrusion is formed strands, spray volume
Instability, the cut-out of strands takes place frequently.It addition, on the surface of the sheath formed by this chlorinated polyethylene composition, confirm not
Smooth situation and be regarded as the convex grain (projection) generated because of the excessive cross-linking reaction of locality.It is explained
Being to confirm in comparative example 4, the gel fraction after crosslinking is 89%, is the high degree of cross linking.
It is explained, in the present embodiment, use is had by H2C=C (CH3) methacryl that represents of-CO-
The situation of the silane compound of base is illustrated, and but it is believed that, even having by H2The acryloyl that C=CH-CO-represents
The silane compound of base, it is also possible to obtain same effect.
The summary ＞ of ＜ embodiments of the present invention
In following [1]～[5], summarize embodiments of the present invention.
[1] a kind of Silane Grafted chlorinated polyethylene, it utilizes peroxide will have by H2C=C (CH3)-CO-represents
The silane compound graft copolymerization of methylacryloyl forms in chlorinated polyethylene, is set to by the molal quantity of aforementioned silane compounds
X, the molal quantity of aforementioned peroxide is set to y, time the quantity of oxygen contained in aforementioned peroxide with the key of oxygen is set to α,
X/2 α y is less than more than 1.5 20.0, and the gel fraction after crosslinking is more than 60%.
[2] the Silane Grafted chlorinated polyethylene of [1], wherein, aforementioned silane compounds comprises 3-methacryloxy third
Base trimethoxy silane or 3-methacryloxypropyl.
[3] manufacture method of a kind of Silane Grafted chlorinated polyethylene, it has peroxide is made an addition to chlorinated polyethylene
Interpolation operation and have by H by adding in aforementioned chlorinated polyethylene2C=C (CH3) methacryl that represents of-CO-
The silane compound of base, thus by aforementioned silane compounds graft copolymerization in the grafting operation of aforementioned chlorinated polyethylene,
In foregoing graft operation, the molal quantity of aforementioned silane compounds is set to x, by the molal quantity of aforementioned peroxide
It is set to y, time the quantity of oxygen contained in aforementioned peroxide with the key of oxygen is set to α, becomes more than 1.5 20.0 according to x/2 α y
Following mode adds aforementioned silane compounds, is carrying out foregoing graft operation after aforementioned interpolation operation.
[4] a kind of insulated electric conductor, it possesses conductor, the insulating barrier arranged in the way of surrounding the periphery of aforementioned conductor, is somebody's turn to do
Insulating barrier is formed by Silane Grafted chlorinated polyethylene, and this Silane Grafted chlorinated polyethylene is to utilize peroxide will have by H2C
=C (CH3) the silane compound graft copolymerization of methylacryloyl that represents of-CO-forms in chlorinated polyethylene, by aforementioned silane
The molal quantity of compound is set to x, the molal quantity of aforementioned peroxide is set to y, by oxygen contained in aforementioned peroxide and oxygen
The quantity of key when being set to α, x/2 α y is less than more than 1.5 20.0, and the gel fraction of described insulating barrier is more than 60%.
[5] a kind of cable, it possess conductor, the insulating barrier arranged in the way of surrounding the periphery of aforementioned conductor, to surround
The surrounding layer that the mode of the periphery of aforementioned dielectric layer is arranged, this surrounding layer is formed by Silane Grafted chlorinated polyethylene, and this silane connects
Branch chlorinated polyethylene is to utilize peroxide will have by H2C=C (CH3) the silane chemical combination of methylacryloyl that represents of-CO-
Graft copolymers forms in chlorinated polyethylene, the molal quantity of aforementioned silane compounds is set to x, by aforementioned peroxide mole
Number is set to y, time the quantity of oxygen contained in aforementioned peroxide with the key of oxygen is set to α, x/2 α y is less than more than 1.5 20.0,
The gel fraction of described cable is more than 60%.
Industrial applicability
Present invention can be suitably applied to use insulated electric conductor and the cable of Silane Grafted chlorinated polyethylene.
Symbol description
1 cable
2 insulated electric conductors
10 conductors
11 insulating barriers
12 sheaths
Claims (5)
1. a Silane Grafted chlorinated polyethylene, it utilizes peroxide will have by H2C=C (CH3) methyl-prop that represents of-CO-
The silane compound graft copolymerization of enoyl-forms in chlorinated polyethylene,
The molal quantity of described silane compound is set to x, the molal quantity of described peroxide is set to y, by described peroxide
In the quantity of contained oxygen and the key of oxygen when being set to α, x/2 α y is less than more than 1.5 20.0, and the gel fraction after crosslinking is 60%
Above.
Silane Grafted chlorinated polyethylene the most according to claim 1, wherein,
Described silane compound comprises 3-methacryloxypropyl trimethoxy silane or 3-methacryloxypropyl
Triethoxysilane.
3. a manufacture method for Silane Grafted chlorinated polyethylene, it has:
Peroxide is made an addition to the interpolation operation of chlorinated polyethylene, and
Have by H by adding in described chlorinated polyethylene2C=C (CH3) silanization of methylacryloyl that represents of-CO-
Compound, thus by described silane compound graft copolymerization in the grafting operation of described chlorinated polyethylene；
In described grafting operation, the molal quantity of described silane compound is being set to x, the molal quantity of described peroxide is being set
When quantity for y, by oxygen contained in described peroxide with the key of oxygen is set to α, according to x/2 α y become more than 1.5 20.0 with
Under mode add described silane compound,
Described grafting operation is being carried out after described interpolation operation.
4. an insulated electric conductor, its comprise conductor and in the way of surrounding the periphery of described conductor the insulating barrier that arranges,
This insulating barrier is formed by Silane Grafted chlorinated polyethylene, and this Silane Grafted chlorinated polyethylene is to utilize peroxide to have
By H2C=C (CH3) the silane compound graft copolymerization of methylacryloyl that represents of-CO-forms in chlorinated polyethylene, by institute
State the molal quantity of silane compound to be set to x, the molal quantity of described peroxide is set to y, by contained in described peroxide
When the quantity of the key of oxygen and oxygen is set to α, x/2 α y is less than more than 1.5 20.0,
The gel fraction of this insulating barrier is more than 60%.
5. a cable, it comprises conductor, the insulating barrier arranged in the way of surrounding the periphery of described conductor and to surround institute
The surrounding layer that the mode of the periphery stating insulating barrier is arranged,
This surrounding layer is formed by Silane Grafted chlorinated polyethylene, and this Silane Grafted chlorinated polyethylene is to utilize peroxide to have
By H2C=C (CH3) the silane compound graft copolymerization of methylacryloyl that represents of-CO-forms in chlorinated polyethylene, by institute
State the molal quantity of silane compound to be set to x, the molal quantity of described peroxide is set to y, by contained in described peroxide
When the quantity of the key of oxygen and oxygen is set to α, x/2 α y is less than more than 1.5 20.0,
The gel fraction of this surrounding layer is more than 60%.
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 |
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| CN106232647A true CN106232647A (en) | 2016-12-14 |
| CN106232647B 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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| JP (1) | JP6187368B2 (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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1365377A (en) * | 1999-07-30 | 2002-08-21 | Nok株式会社 | Molding material for carbon dioxide |
Family Cites Families (2)
| 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 |
| 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
- 2015-03-26 CN CN201580022355.3A patent/CN106232647B/en active Active
- 2015-03-26 WO PCT/JP2015/059429 patent/WO2015152005A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN1365377A (en) * | 1999-07-30 | 2002-08-21 | Nok株式会社 | Molding material for carbon dioxide |
Non-Patent Citations (1)
| Title |
|---|
| 谢德伦: "《橡胶挤出成型》", 31 October 2005 * |
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| JP2015199795A (en) | 2015-11-12 |
| WO2015152005A1 (en) | 2015-10-08 |
| CN106232647B (en) | 2019-08-09 |
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