CN109503906A - A kind of powerful permanent seal cooling flame-proof power cable sheath and preparation method thereof - Google Patents
A kind of powerful permanent seal cooling flame-proof power cable sheath and preparation method thereof Download PDFInfo
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- CN109503906A CN109503906A CN201811399938.XA CN201811399938A CN109503906A CN 109503906 A CN109503906 A CN 109503906A CN 201811399938 A CN201811399938 A CN 201811399938A CN 109503906 A CN109503906 A CN 109503906A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a kind of powerful permanent seal cooling flame-proof power cable sheaths and preparation method thereof, mix butadiene-styrene rubber and natural rubber, and stirring is in emulsion state；Silicone oil, nano zine oxide, stearic acid, sulphur powder, anti-aging agent, promotor, spray carbon black and adjacent dibutyl ester are mixed, is dispersed with stirring and is then added in latex, be kneaded to obtain rubber compound；Silica modified additive is added into rubber compound, second is kneaded up to final sizing material.The attapulgite powder of silica particles has dispersibility well under silane resin acceptor kh-550 effect, and the toughness and tensile characteristics of finished product sizing material can be improved, after silica dioxide granule is combined by silane resin acceptor kh-550 with attapulgite powder grafting, it can be good at being present in rubber mass, improve the flame-retarding characteristic of cable cover(ing).
Description
Technical field
The present invention relates to the technical field of power cable more particularly to a kind of powerful permanent seal cooling flame-proof power cable sheath and
Preparation method.
Background technique
Silica is widely used in fields such as rubber, plastics, catalyst carrier, adsorbent, biological medicines, usually needs
It is compound with organic matrix, still, with other inorganic, metal oxides as aluminium oxide, titanium dioxide, zinc oxide etc., dioxy
There is great amount of hydroxy group on SiClx surface, and hydrophily is strong, the compatibility and bad dispersibility compound with organic matrix, it is difficult to it is excellent to play its
Performance, it is necessary to which organic decoration is carried out to its surface.Gamma-aminopropyl-triethoxy-silane (APTS) is a kind of typical silane coupled
Agent is usually used in the modification of oxide surface, contains amino by the surface that APTS is modified, active amino can be sent out with many molecules
Raw reaction, to significantly expand and improve the application performance of silica.Titanium dioxide such as after chemical material field, modification
Silicon particle is added to rubber as reinforced filling, in plastic or other material, can effectively improve the tensile strength, wear-resisting of complex matrix
The performances such as property, rheological characteristic, anti-aging.
Related clay mineral is modified and as filler, and the report for enhancing the polymer composites such as rubber is more.It will such as stick
Soil-silane coupling agent is distributed in butadiene-styrene rubber (SBR) lotion, and through flocculation, drying, mixing, 300% that vulcanization SBR is made is drawn
It stretches the pure SBR of modular ratio and improves 8 times or more, it is more than black-reinforced SBR that tensile strength, which improves 7 times or more,.
Present invention mainly solves be in cable cover(ing) add good flame resistance inorganic powder, cause anti-flammability although to mention
The problem of high but pull resistance reduces.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of powerful permanent seal cooling flame-proof power cable sheath and its preparation sides
Method, it is main to be to solve the inorganic powder that good flame resistance is added in cable cover(ing), although anti-flammability is caused to improve tension
Property reduce the problem of.
The present invention is realized by following technological means solves above-mentioned technical problem:
First by three ethoxyethyl silane (APTS) of coupling agent γ-aminopropyl, it is silane resin acceptor kh-550, also with toluene
The attapulgite powder of its total amount 20~30% is then added, in water-bath in shaking up after the ratio mixing of 1:50~60 as solvent
80~100min is stirred at reflux under the conditions of 60~80 DEG C；It filters, wash and is dried under the conditions of 110 DEG C after the completion.
The silica dioxide granule that preparation partial size is 1~2mm, is first put into 6wt%'s according to the ratio of solid-liquid ratio 1:15~20
In hydrofluoric acid buffer solution, 5~8min of pickling is washed 2~3 times after the completion, drying；Then by silica dioxide granule in reaction kettle
200~300 DEG C of preheatings 2~3min of rolling of high temperature, then using toluene as solvent, configuration concentration is 5~8% silane coupling agents
KH-550 solution is added in the ratio of solid-liquid ratio 1:40~50 into previous reaction kettle, under the conditions of 60~80 DEG C, with 800~
1200r/min 20~30min of mixing speed stirring and adsorbing grafting is completed, and is added water and stirred and is washed to remaining silica dioxide granule
It washs, the water of material total amount 10~20% in reaction kettle is retained after washing, aforementioned modified attapulgite is then added by 6:1
Powder stirs 30~50min with 800~1200r/min, obtains silica modified additive under the conditions of 60~80 DEG C.
The sheath of power cable of the present invention, for main latex, mainly includes the original that following parts by weight are unit with butadiene-styrene rubber
Material: 100~120 parts of butadiene-styrene rubber, 30~40 parts of silica modified additive, 20~30 parts of natural rubber, 2~5 parts of silicone oil,
2~4 parts of nano zine oxide, 2~6 parts of sulphur powder, 1~2 part of anti-aging agent RD, 1~3 part of accelerant CZ, is sprayed 1~3 part of stearic acid
10~20 parts of 10~15 parts of carbon black and plasticizer neighbour dibutyl ester.
(1) butadiene-styrene rubber and natural rubber are mixed, stirring is in emulsion state under the conditions of 300~400r/min；
(2) silicone oil, nano zine oxide, stearic acid, sulphur powder, anti-aging agent, promotor, spray carbon black and adjacent two fourths are mixed
Ester, is dispersed with stirring 6~8h under the conditions of 800~1200r/min, is then added into the latex of (1), in the first compounding conditions
For in 150~220 DEG C, the reaction kettle of 10~12MPa, 10~15min of stirring obtains rubber compound；
(3) after the completion of (2), silica modified additive is added into rubber compound obtained by (2), setting second is kneaded
Condition is 180~300 DEG C, 10~15MPa, and 20~30min of stirring obtains molten state rubber mass, 180~220 DEG C of heat preservation, stirring
Under the conditions of 100~150r/min of axis revolving speed, keeps rubber mass to uniformly introduce plastic extruder, the thickness 8mm of extrude sheath is set,
Traction device trailing cable becomes cable cover(ing) by the surface that head is extruded in cable by head, by rubber mass, cold immediately
But.
Just have in the early time in catalytic field, the silica mesoporous zeolite of amination modification can be realized amines catalyst
It is immobilized, be then catalyzed and obtained the example of fine achievement, the present invention by using the silica of bulky grain (partial size 1~
2mm) as the filler of rubber, it is subsequently used for the preparation of power cable sheath layer.
The modification of APTS is substantially absorption and reaction of the APTS in silica surface.APTS and silica
Reaction can be divided into anhydrous and have two kinds of situations of water, and under that condition of water, APTS can be hydrolyzed, and ethyoxyl, which first hydrolyzes, becomes hydroxyl, then
It is reacted with silica surface hydroxyl, dehydration forms Si-O-Si key, after the hydrolysis of formula APTS molecule, 3 of APTS molecule
Ethoxy group is optionally substituted by a hydroxyl group, and is caused hydrolysate to be easy mutually condensation, is formed silicones, or in silica
Surface condensation forms irregular APTS polymolecular decorative layer.Be grafted between the APTS molecule of particle surface it can also happen that
Cross-linking can generate irregular polymolecular layer.
Attapulgite powder, purity >=95%, 10~50nm of diameter, the raphioid fiber of length < 5um, purification attapulgite tool
There is large specific surface area, suspension is good, and the strong feature of adsorption capacity, attapulgite surface contains a large amount of silicone hydroxyls, causes it in rubber
It is easy to reunite in matrix body.To improve attapulgite on the dispersibility in rubber and the boundary between attapulgite and rubber molecule
Face binding force gives full play to reinforcing effect of the nano-attapulgite to rubber, is generally carried out with silane coupling agent to attapulgite
Surface organic modification.
The present invention has the advantages that the present invention utilizes attapulgite powder and silica dioxide granule and silane coupling agent simultaneously
KH-550 is grafted, and silica therein is not the powdered of mesh number very little, but the graininess with certain partial size, benefit
Smooth silica particles are corroded with hydrofluoric acid, form the surface of silica dioxide granule rough recessed
Slot makes the surface of silica become coarse, is conducive to the absorption of silane resin acceptor kh-550 active function groups；Attapulgite powder
It is also common cable additive, for improving the toughness of cable rubber, in repeatedly pullling, keeps cable surface layer sheath still
Situations such as will not cracking；The additive effect that attapulgite is directly used in cable rubber mass is poor, and reason is that attapulgite powder is
Rod-like fibre is combined together after being easy accumulation, is unfavorable for being dispersed in rubber mass, is made by adding silane resin acceptor kh-550
The dispersibility of attapulgite powder is more uniform.
The present invention forms latticed space structure, so for after attapulgite powder and silane resin acceptor kh-550 grafting complexing
It is mixed afterwards with silica dioxide granule modified, so that attapulgite powder is adsorbed onto the surface of silica, due to dioxy
The surface of silicon carbide particle carries out peracid treatment, has groove on the surface of silica dioxide granule, attapulgite powder can be embedded in
On the groove of silica surface, since silica and attapulgite powder all there is grafting to adsorb silane resin acceptor kh-550
Performance, therefore silica and attapulgite powder can be integrated to one piece by intermediate silane coupling agent KH-550, have steady
Fixed property.
With butadiene-styrene rubber for main sizing material, by adding auxiliary material, reaches plasticising, reinforcement, age inhibiting effect, then add
Silica modified additive, by secondary mixing, the attapulgite powder of silica particles is in silane coupling agent KH-
550 effects are lower to have dispersibility well, and the toughness and tensile characteristics of finished sheath can be improved, silica dioxide granule category
, here can not be directly in conjunction with rubber, after being combined by silane resin acceptor kh-550 with attapulgite powder grafting in bulky grain, energy
It is enough to be present in rubber mass well, improve the flame-retarding characteristic of cable cover(ing).
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in the embodiment of the present invention
Technical solution is clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than complete
The embodiment in portion.Based on the embodiments of the present invention, those of ordinary skill in the art are without creative efforts
Every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment:
First by three ethoxyethyl silane (APTS) of coupling agent γ-aminopropyl, it is silane resin acceptor kh-550, also with toluene
The attapulgite powder of its total amount 25% is then added, in 70 DEG C of conditions of water-bath in shaking up after the ratio mixing of 1:55 as solvent
Under be stirred at reflux 90min；It filters, wash and is dried under the conditions of 110 DEG C after the completion.
The silica dioxide granule that preparation partial size is 1mm, the hydrofluoric acid for being first put into 6wt% according to the ratio of solid-liquid ratio 1:16 are slow
It rushes in solution, pickling 6min, washes 2 times after the completion, drying；Then silica dioxide granule is pre- in 250 DEG C of reaction kettle high temperature
Heat rolling 2min, then using toluene as solvent, configuration concentration is 6% silane resin acceptor kh-550 solution, by solid-liquid ratio 1:45's
Ratio is added into previous reaction kettle, under the conditions of 70 DEG C, is grafted and is completed with 1000r/min mixing speed stirring and adsorbing 25min,
It adds water and stirs and remaining silica dioxide granule is washed, the water of material total amount 15% in reaction kettle is retained after washing, then so
Aforementioned modified attapulgite powder is added by 6:1 afterwards, under the conditions of 70 DEG C, 40min is stirred with 1000r/min, obtains titanium dioxide
Si modification additive.
The sheath of power cable of the present invention, for main latex, is mainly unit including following weight (Kg) with butadiene-styrene rubber
Raw material: butadiene-styrene rubber 110Kg, silica modified additive 35Kg, natural rubber 25Kg, silicone oil 4Kg, nano zine oxide
Adjacent two fourths of 3Kg, 1~3Kg of stearic acid, sulphur powder 5Kg, anti-aging agent RD 1Kg, accelerant CZ 2Kg, spray carbon black 12Kg and plasticizer
Ester 15Kg.
(1) butadiene-styrene rubber and natural rubber are mixed, stirring is in emulsion state under the conditions of 350r/min；
(2) silicone oil, nano zine oxide, stearic acid, sulphur powder, anti-aging agent, promotor, spray carbon black and adjacent two fourths are mixed
Ester, is dispersed with stirring 7h under the conditions of 1000r/min, is then added into the latex of (1), the first compounding conditions be 200 DEG C,
In the reaction kettle of 10MPa, stirring 10min obtains rubber compound；
(3) after the completion of (2), silica modified additive is added into rubber compound obtained by (2), setting second is kneaded
Condition is 250 DEG C, 12MPa, and stirring 25min obtains molten state rubber mass, keeps the temperature 190 DEG C, agitator shaft speed 120r/min condition
Under, it keeps rubber mass to uniformly introduce plastic extruder, the thickness 8mm of extrude sheath is set, and traction device trailing cable passes through machine
Rubber mass is become cable cover(ing) by the surface that head is extruded in cable, cooled down immediately by head.
Sizing material of the invention is passed through and extrudes the oversheath that power cable is made, the general oversheath electric power electricity in setting market
Its various aspects of performance is comprehensively compared in cable, and wear-resisting property, fire resistance property, which all have, to be obviously improved, in terms of tension liter, although this
The tensile property of invention does not protrude, but can be competent at completely under conditions of not being extreme stretch.
It should be noted that, in this document, such as first and second or the like relational terms are used merely to one if it exists
A entity or operation with another entity or operate distinguish, without necessarily requiring or implying these entities or operation it
Between there are any actual relationship or orders.Moreover, the terms "include", "comprise" or its any other variant are intended to
Cover non-exclusive inclusion, so that the process, method, article or equipment for including a series of elements not only includes those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or setting
Standby intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in the process, method, article or apparatus that includes the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (5)
1. a kind of powerful permanent seal cooling flame-proof power cable sheath, it is characterised in that: be made of following parts by weight of the raw material of unit:
100~120 parts of butadiene-styrene rubber, 20~30 parts of natural rubber, 2~5 parts of silicone oil, is received 30~40 parts of silica modified additive
2~4 parts of zinc oxide of rice, 2~6 parts of sulphur powder, 1~2 part of anti-aging agent RD, 1~3 part of accelerant CZ, is sprayed 1~3 part of stearic acid
10~20 parts of 10~15 parts of carbon black and plasticizer neighbour dibutyl ester.
2. a kind of preparation method of powerful permanent seal cooling flame-proof power cable sheath, it is characterised in that: including following steps,
(1) butadiene-styrene rubber and natural rubber are mixed, stirring is in emulsion state under the conditions of 300~400r/min；
(2) silicone oil, nano zine oxide, stearic acid, sulphur powder, anti-aging agent, promotor, spray carbon black and adjacent dibutyl ester are mixed,
Be dispersed with stirring 6~8h under the conditions of 800~1200r/min, be then added into the latex of (1), the first compounding conditions be 150~
220 DEG C, in the reaction kettle of 10~12MPa, 10~15min of stirring obtains rubber compound；
(3) silica modified additive, the silica dioxide granule that preparation partial size is 1~2mm, by surface preparation are configured
Afterwards, silica dioxide granule after pretreatment is carried out to the grafting of silane resin acceptor kh-550, water content is 10~20% after cleaning, so
The attapulgite powder being dried to obtain after attapulgite powder and silane resin acceptor kh-550 grafting is added in the ratio of 6:1~2 afterwards,
Under the conditions of 60~80 DEG C, 30~50min is stirred with 800~1200r/min, obtains silica modified additive.
(4) after the completion of (2), silica modified additive is added into rubber compound obtained by (2), the second compounding conditions are set
For 180~300 DEG C, 10~15MPa, stirs 20~30min and obtain molten state rubber mass, 180~220 DEG C of heat preservation, agitating shaft turn
It under the conditions of 100~150r/min of speed, keeps rubber mass to uniformly introduce plastic extruder, the thickness 8mm of extrude sheath is set, draw
Device trailing cable becomes cable cover(ing) by the surface that head is extruded in cable by head, by rubber mass, and cooling immediately is
It can.
3. a kind of preparation method of powerful permanent seal cooling flame-proof power cable sheath according to claim 2, it is characterised in that: institute
Stating attapulgite powder and carrying out the condition of the grafting of silane resin acceptor kh-550 is to press coupling agent KH-550 using toluene as solvent
It is shaken up after the ratio mixing of 1:50~60, the attapulgite powder of its total amount 20~30% is then added, in 60~80 DEG C of items of water-bath
It is stirred at reflux 80~100min under part, filters after the completion, wash and is dried under the conditions of 110 DEG C.
4. a kind of preparation method of powerful permanent seal cooling flame-proof power cable sheath according to claim 2, it is characterised in that: institute
Stating the pretreated condition of silica is put into the hydrofluoric acid buffer solution of 6wt% according to the ratio of solid-liquid ratio 1:15~20,
5~8min of pickling is washed 2~3 times after the completion, drying, finally in 200~300 DEG C of 2~3min of preheatings rolling of reaction kettle high temperature
It obtains.
5. a kind of preparation method of powerful permanent seal cooling flame-proof power cable sheath according to claim 2, it is characterised in that: institute
Stating silica dioxide granule and carrying out the condition of the grafting of silane resin acceptor kh-550 is by pretreated silica dioxide granule with toluene
For solvent, configuration concentration is 5~8% silane resin acceptor kh-550 solution, and pretreatment is added in the ratio of solid-liquid ratio 1:40~50
Silica dioxide granule, in reaction kettle under the conditions of 60~80 DEG C, connect with 800~1200r/min mixing speed stirring and adsorbing
20~30min of branch is completed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811399938.XA CN109503906A (en) | 2018-11-22 | 2018-11-22 | A kind of powerful permanent seal cooling flame-proof power cable sheath and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811399938.XA CN109503906A (en) | 2018-11-22 | 2018-11-22 | A kind of powerful permanent seal cooling flame-proof power cable sheath and preparation method thereof |
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| CN109503906A true CN109503906A (en) | 2019-03-22 |
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| CN201811399938.XA Pending CN109503906A (en) | 2018-11-22 | 2018-11-22 | A kind of powerful permanent seal cooling flame-proof power cable sheath and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110565370A (en) * | 2019-10-09 | 2019-12-13 | 苏州经贸职业技术学院 | preparation method of natural flame-retardant finishing agent |
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| CN102532630A (en) * | 2011-12-23 | 2012-07-04 | 北京化工大学 | Preparation method of styrene butadiene rubber liquid slurry added with white carbon black and product prepared by using same |
| CN106397857A (en) * | 2016-08-31 | 2017-02-15 | 安徽宏源特种电缆股份有限公司 | High-strength cold-resistance soft rubber sheath material |
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| 《橡胶工业手册》编写小组编写: "《橡胶工业手册 第3分册 基本工艺》", 31 August 1976, 石油化学工业出版社 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110565370A (en) * | 2019-10-09 | 2019-12-13 | 苏州经贸职业技术学院 | preparation method of natural flame-retardant finishing agent |
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