CN108586954A - A kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube and preparation method thereof - Google Patents
A kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube and preparation method thereof Download PDFInfo
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- CN108586954A CN108586954A CN201810463359.0A CN201810463359A CN108586954A CN 108586954 A CN108586954 A CN 108586954A CN 201810463359 A CN201810463359 A CN 201810463359A CN 108586954 A CN108586954 A CN 108586954A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2203/18—Applications used for pipes
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Abstract
The present invention relates to a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tubes, belong to the preparation field of EP rubbers cold shrink tube.The cold shrink tube includes the component of following parts by weight：80 100 parts of EP rubbers, 10 30 parts of based elastomers, 2 10 parts of zinc oxide, 0.2 2 parts of stearic acid, 5 50 parts of carbon black, 5 50 parts of white carbon, 10 150 parts of fire retardant, 15 60 parts of flame retardant, 10 40 parts of filler；8 40 parts of plasticizer, 15 parts of processing aid, 0.4 5 parts of coupling agent, 2.5 10 parts of vulcanizing agent, 0.2 10 parts of auxiliary curing agent, 04 parts of anti-aging agent.The preparation method of the present invention is simple and convenient to operate, low in raw material price, and no toxic chemical substance participates in, environmentally protective.Meanwhile halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube prepared by the present invention has excellent LSOH anti-flaming performance and electrical insulation capability.
Description
Technical field
The present invention relates to the preparation field of EP rubbers cold shrink tube more particularly to a kind of halogen-free flame-retardant environment-friendly EP rubbers
Cold shrink tube and preparation method thereof.
Background technology
Cold shrink tube generally refers to the rubber tube using cold events technology, has the function of excellent insulation, sealing, protection etc..
Because it is to lean on elastic recovery force to shrink at normal temperatures, without being heated, therefore referred to as cold events.Simultaneously again due to its body
Product it is small, easy to operate, without as heat-shrinkable T bush is applied when need special heating tool, have a wide range of application, be mainly used in electricity
The end of insulation protection that power cable, communication cable and optical cable connect, fire-retardant, waterproof, moisture seal, wireless telecommunications tower and exposure
The connection of end, connector, antenna etc., implement handle, pipeline rehabilitation or other kinds of sealing.
Currently, the common material of cold shrink tube has silicon rubber and EP rubbers, but find in long-term use, by silicon rubber system
At the resistance to acid and alkali of cold shrink tube, moisture resistance, wearability, anti-flammability it is not ideal and of high cost.And EP rubbers
Mechanical performance and electrical insulation capability are excellent, and resistance to weather, resistance to ozone aging, UV resistant performance are good, and high and low temperature resistance, water-fast
It is property, excellent to the adaptability of processing technology etc., it is the ideal of communication cable, coaxial cable, medium-low voltage power cable, flame retardant cable
Sealing material, however, the flame retardant property of existing EP rubbers cold shrink tube is bad, it is easy to cause fire to cause heavy losses,
The glue cold shrink tube and preparation method thereof with anti-flammability that therefore, it is necessary to study a kind of.
Invention content
For the above-mentioned prior art the problem of, the present invention is intended to provide a kind of halogen-free flame-retardant environment-friendly EP rubbers
Cold shrink tube and preparation method thereof.Halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube prepared by the present invention not only has excellent fire-retardant
Performance and electrical insulation capability, and resistance to weather, resistance to ozone aging, UV resistant performance are good, and water resistance and high and low temperature resistance are excellent
It is different；Meanwhile preparation method of the invention is simple and convenient to operate, production cost is low, it is easy to accomplish large-scale production.
An object of the present invention is to provide a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
For achieving the above object, specifically, the invention discloses following technical proposals：
A kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, by weight, including following components：
The EP rubbers includes：One kind in bibasic ethylene propylene rubber, ethylene propylene diene rubber, oil extended EPDM or
It is a variety of.
Preferably, the Mooney viscosity of the EP rubbers is 25-65, contents of ethylene 48%-73%, Third monomer
ENB contents are 0-10%, remaining is acrylic content.
The based elastomers are ethylene-vinyl acetate copolymer, wherein VA (vinyl acetate) content is in 18%-
Between 70%.
The carbon black includes：It is one or more in N330, N550, N660, N774, N990, spray carbon black.
The white carbon includes the mixture of one or both of fume colloidal silica, precipitated silica.Preferably,
The specific surface area of the white carbon is 50-200m2/g。
The fire retardant includes：Aluminium hydroxide, magnesium hydroxide, hydrotalcite, melamine cyanurate, hypo-aluminum orthophosphate, phosphorus
Sour three monooctyl esters, tricresyl phosphate, encapsulated red phosphorus, aluminum diethylphosphinate, expansible graphite, ammonium polyphosphate, pentaerythrite, three
It is one or more in poly cyanamid.
The flame retardant includes：In zinc borate, mica powder, montmorillonite powder, silicone, attapulgite, vermiculite power, alumina silicate
It is one or more.
The filler includes：It is one or more in calcium carbonate, talcum powder, kaolin, diatomite.
The plasticizer includes：Paraffin oil, dioctyl phthalate, dioctyl sebacate, dioctyl adipate, low point
It is one or more in son amount polyisobutene, Liquid Ethylene Propylene Methylene aromatic naphtha, naphthenic oil, dibutyl phthalate.
The processing aid includes：It is one or more in polyethylene glycol, WB42, polyethylene wax, WA48, WB212.
The coupling agent includes：Vinyltriethoxysilane, vinyltrimethoxysilane, three (beta-methoxy of vinyl
Base oxethyl) silane, γ-methacryloxypropyl trimethoxy silane, γ-mercapto oxypropyl trimethyl silane, γ-mercapto propyl
Triethoxysilane, bis- (γ-triethoxysilylpropyl)-tetrasulfides, one kind in gamma-aminopropyl-triethoxy-silane or more
Kind.
The vulcanizing agent is peroxide, including：Cumyl peroxide, 1,4- bis- (t-butylperoxy diisopropyls)
Bis- (t-butylperoxy diisopropyl) benzene of benzene, 1,4-, 2,5- dimethyl -2,5- (di-t-butyl peroxy) hexane, 2,5- bis-
Methyl -2,5- (di-t-butyl peroxy) -3- hexins, bis- tert-butyl peroxy base -3,3,5- trimethoxies hexamethylenes of 1,1-, 4,4- are bis-
It is one or more in (tert-butyl peroxy base) n-butyl pentanoate.
The vulcanization aid includes：It is triallylcyanurate, trihydroxy methyl propane trimethyl acrylate, Sulfur, double
Methacrylic acid glycol ester, N, the bis- furfurylidene-acetones of N`-, N, N`- meta-phenylene bismaleimides, dimethacrylate
It is one or more in zinc, Triallyl isocyanurate, triallyltrimelitate.
The anti-aging agent includes：Nickel dibutyl dithiocarbamate, the polymerization of 2,2,4- trimethyl -1,2- dihyaroquinolines
Body, N- isopropyls-N '-diphenyl-para-phenylene diamine, acetone and one kind in diphenylamines high-temperature reaction product, 2-mercaptobenzimidazole or
It is a variety of.
The second object of the present invention is to provide a kind of preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
For achieving the above object, specifically, the invention discloses following technical proposals：
A kind of preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, specifically comprises the following steps：
(1) first, according to each component and its weight ratio, EP rubbers and based elastomers are plasticated；So
Afterwards be added zinc oxide, stearic acid, anti-aging agent, processing aid, white carbon, coupling agent, carbon black, fire retardant, flame retardant, filler,
Plasticizer, vulcanizing agent and vulcanization aid are kneaded uniform aftershaping；
(2) product after molding in step 1) is vulcanized, the tubing vulcanizated is clipped, expansion is simultaneously built-in supports
Pipe, you can obtain halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
In step 1), the molding includes：Extrusion molding or injection moulding.
In step 2), the mode of the vulcanization includes：Molding vulcanization, drying tunnel vulcanization, vulcanization digester (-tor) high temperature and pressure vulcanization or
Salt bath vulcanization.
Low inflaming retarding ethylene propylene rubber cold shrink tube, it is characterised in that：The cold shrink tube includes the component of following parts by weight：The third rubber of second
80-100 parts of glue, 10-30 parts of based elastomers, 2-10 parts of zinc oxide, 0.2-2 parts of stearic acid, 5-50 parts of carbon black, white carbon 5-
50 parts, it is 10-150 parts of fire retardant, 15-60 parts of flame retardant, 10-40 parts of filler, 8-40 parts of plasticizer, 1-5 parts of processing aid, even
Join 0.4-5 parts of agent, 2.5-10 parts of vulcanizing agent, 0.2-10 parts of auxiliary curing agent, 0-4 parts of anti-aging agent；
The third object of the present invention is to provide a kind of low inflaming retarding ethylene propylene rubber cold shrink tube, the low inflaming retarding ethylene propylene rubber shrinkage
Pipe has the following performance：Hardness, Shao Er A：40-70；Tensile strength, MPa：9-13；Tearing strength, KN/m：25-49；Fracture is stretched
Long rate, %：550-900；Volume resistivity, Ω cm：1014-1016；Dielectric constant：2.8-3.2；Electrical strength, KV/mm：
19-24；Flame retardant rating, UL94V0.
The fourth object of the present invention is to provide halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube and preparation method thereof and low
The application of inflaming retarding ethylene propylene rubber cold shrink tube is included in communication cable, coaxial cable, medium-low voltage power cable, flame retardant cable
Using.
It should be noted that in order to make EP rubbers cold shrink tube obtain flame retardant property, and with being intended to EP rubbers cold shrink tube
Component in addition fire retardant and flame retardant can seriously affect the mechanical property of product, lead to tensile strength, the tearing of product
Intensity, elongation at break etc. significantly decline, or even not up to standard, to solve the above-mentioned problems, make the EP rubbers shrinkage of preparation
Pipe has both excellent good mechanical property and flame retardant property, and the present invention has carried out the component and its content of EP rubbers cold shrink tube excellent
Change, make to produce good synergistic effect between fire retardant and other auxiliary agents, not only improve product in combustion at
The flame retardant property of product is greatly improved in charcoal situation, and does not influence the mechanical property of product, or even can also be to mechanical property
It is promoted.
Compared with prior art, the advantageous effect that the present invention obtains is：
(1) preparation method of the invention is simple and convenient to operate, low in raw material price, and no toxic chemical substance participates in, green
Environmental protection.Meanwhile halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube prepared by the present invention has excellent LSOH anti-flaming performance
And electrical insulation capability, and resistance to weather, cold resistance and the ozone aging resistance of the diaphragm, UV resistant performance are good, and water resistance and high and low temperature resistance are excellent
It is elegant.
(2) halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube prepared by the present invention obtains following performance：Hardness, Shao Er A：
40-70；Tensile strength, MPa：9-13；Tearing strength, KN/m：25-49；Elongation at break, %：550-900；Volume resistivity,
Ω·cm：1014-1016；Dielectric constant：2.8-3.2；Electrical strength, KV/mm：19-24；Flame retardant rating, UL94V0.Wherein, it hinders
In the test for firing performance, after carrying out 10 seconds combustion testings twice to sample, flame extinguishes in 3 seconds and without any comburant
It falls down, it can be seen that product of the invention has excellent LSOH anti-flaming performance.
Specific implementation mode
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used herein has usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe specific implementation mode, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or combination thereof.
As background technology is introduced, the flame retardant property of existing EP rubbers cold shrink tube is bad, it is easy to cause fire
Calamity causes heavy losses, and therefore, the present invention proposes a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube and preparation method thereof,
The present invention is described further With reference to embodiment.
Embodiment 1
1, a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, the cold shrink tube include the ingredient of following parts by weight：Two
70 parts of first EP rubbers, 30 parts of ethylene propylene diene rubber, 10 parts of ethylene-vinyl acetate copolymer, 5 parts of zinc oxide, stearic acid 1
Part, 50 parts of carbon black N330,10 parts of fume colloidal silica, 90 parts of aluminium hydroxide, 10 parts of trioctyl phosphate, 30 parts of mica powder, carbonic acid
10 parts of calcium, 20 parts of paraffin oil, 5 parts of WB212,3 parts of vinyltriethoxysilane, 6 parts of cumyl peroxide, triallyl
0.2 part of cyanurate, 2 parts of 2,2,4- trimethyl -1,2- dihyaroquinolines condensate.
In the present embodiment, the Mooney viscosity of the bibasic ethylene propylene rubber is 50, and contents of ethylene 55%, remaining is propylene
Base content；The Mooney viscosity of ethylene propylene diene rubber is 46, contents of ethylene 52%, and third monomer ENB content is 4.3%.Institute
It is 70% to state VA contents in ethylene-vinyl acetate copolymer.The specific surface area of the white carbon is 200m2/g。
2, a kind of preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, specifically comprises the following steps：
(1) first, according to each component in the present embodiment and its weight ratio, by EP rubbers and based elastomers into
Row is plasticated；Then zinc oxide is added, stearic acid, anti-aging agent, processing aid, white carbon, coupling agent, carbon black, fire retardant, fire-retardant helps
Agent, filler, plasticizer, vulcanizing agent and vulcanization aid, extrusion molding after being kneaded uniformly；
(2) molding vulcanization, 170 DEG C of curing temperature, sulfide stress 12MPa are carried out to product after molding in step 1)；Sulphur
The tubing changed is clipped, expansion and built-in support tube, you can obtains halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
Embodiment 2
1, a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, the cold shrink tube include the ingredient of following parts by weight：It fills
100 parts of oily ethylene propylene diene rubber, 30 parts of ethylene-vinyl acetate copolymer, 5 parts of zinc oxide, 1 part of stearic acid, carbon black N660 35
Part, 25 parts of fume colloidal silica, 70 parts of hydrotalcite, 60 parts of melamine cyanurate, 10 parts of tricresyl phosphate, diethyl time
10 parts of phosphonic acids aluminium, 40 parts of talcum powder, 8 parts of dibutyl phthalate, 2 parts of polyethylene glycol, (the 'beta '-methoxy ethoxy of vinyl three
Base) 5 parts of silane, bis- 6 parts of (t-butylperoxy diisopropyl) benzene of 1,4-, N, 2 parts of N`- meta-phenylene bismaleimides, N-
2.5 parts of isopropyl-N '-diphenyl-para-phenylene diamine.
In the present embodiment, the Mooney viscosity of the oil extended EPDM is 65, contents of ethylene 66.5%, third
Enb monomer content is 4.7%, and oil-filled number is 13 parts.VA contents are 18% in the ethylene-vinyl acetate copolymer.Institute
The specific surface area for stating white carbon is 150m2/g。
2, a kind of preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, specifically comprises the following steps：
(1) first, according to each component in the present embodiment and its weight ratio, by EP rubbers and based elastomers into
Row is plasticated；Then zinc oxide is added, stearic acid, anti-aging agent, processing aid, white carbon, coupling agent, carbon black, fire retardant, fire-retardant helps
Agent, filler, plasticizer, vulcanizing agent and vulcanization aid, extrusion molding after being kneaded uniformly；
(2) salt bath vulcanization is carried out to product after molding in step 1), drying tunnel temperature is 200 DEG C；The tubing warp vulcanizated
It cuts, support tube built in expansion simultaneously, you can obtain halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
Embodiment 3
1, a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, the cold shrink tube include the ingredient of following parts by weight：Three
100 parts of first EP rubbers, 15 parts of ethylene-vinyl acetate copolymer, 5 parts of zinc oxide, 0.5 part of stearic acid, carbon black N990 25
Part, 25 parts of precipitated silica, 75 parts of melamine cyanurate, 25 parts of hypo-aluminum orthophosphate, 15 parts of zinc borate, 15 parts of kaolin,
10 parts of dioctyl adipate, 2 parts of WB42, γ -0.4 part of mercapto oxypropyl trimethyl silane, the positive fourth of bis- (tert-butyl peroxy base) valeric acids of 4,4-
6.5 parts of ester, 2.5 parts of Triallyl isocyanurate, 2 parts of nickel dibutyl dithiocarbamate.
In the present embodiment, the Mooney viscosity of the ethylene propylene diene rubber is 48, contents of ethylene 64%, Third monomer
ENB contents are 8.5%.VA contents are 40% in the ethylene-vinyl acetate copolymer.The specific surface area of the white carbon is
150m2/g。
2, a kind of preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, specifically comprises the following steps：
(1) first, according to each component in the present embodiment and its weight ratio, by EP rubbers and based elastomers into
Row is plasticated；Then zinc oxide is added, stearic acid, anti-aging agent, processing aid, white carbon, coupling agent, carbon black, fire retardant, fire-retardant helps
Agent, filler, plasticizer, vulcanizing agent and vulcanization aid, injection moulding after being kneaded uniformly；
(2) moulding press vulcanization is moved to product after molding in step 1), curing temperature is 170 DEG C；The tubing vulcanizated
Clipped, expansion and built-in support tube, you can obtain halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
Embodiment 4
1, a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, the cold shrink tube include the ingredient of following parts by weight：Two
80 parts of first EP rubbers, 5 parts of zinc oxide, 1 part of stearic acid, 45 parts of carbon black N550, sinks at 20 parts of ethylene-vinyl acetate copolymer
5 parts of shallow lake method white carbon, 60 parts of aluminium hydroxide, 30 parts of magnesium hydroxide, 60 parts of montmorillonite powder, 25 parts of diatomite, 25 parts of paraffin oil,
2 parts of WA48,1.8 parts of γ-methacryloxypropyl trimethoxy silane, 2,5- dimethyl -2,5- (di-t-butyl peroxides
Base) 6.5 parts of -3- hexins, 2.5 parts of ethyleneglycol dimethyacrylate, 2 parts of 2-mercaptobenzimidazole.
In the present embodiment, the Mooney viscosity of the bibasic ethylene propylene rubber is 25, and contents of ethylene 73%, remaining is propylene
Base content.VA contents are 50% in the ethylene-vinyl acetate copolymer.The specific surface area of the white carbon is 50m2/g。
2, a kind of preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, specifically comprises the following steps：
(1) first, according to each component in the present embodiment and its weight ratio, by EP rubbers and based elastomers into
Row is plasticated；Then zinc oxide is added, stearic acid, anti-aging agent, processing aid, white carbon, coupling agent, carbon black, fire retardant, fire-retardant helps
Agent, filler, plasticizer, vulcanizing agent and vulcanization aid, extrusion molding after being kneaded uniformly；
(2) salt bath vulcanization is carried out to product after molding in step 1), curing temperature is 200 DEG C；The tubing warp vulcanizated
It cuts, support tube built in expansion simultaneously, you can obtain halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
Embodiment 5
1, a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, the cold shrink tube include the ingredient of following parts by weight：Three
85 parts of first EP rubbers, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of zinc oxide, 2 parts of stearic acid, 5 parts of carbon black N550, gas
50 parts of phase method white carbon, 60 parts of hydrotalcite, 45 parts of melamine cyanurate, 10 parts of encapsulated red phosphorus, 10 parts of trioctyl phosphate, leech
15 parts of mountain flour, 20 parts of calcium carbonate, 8 parts of dioctyl sebacate, 2.5 parts of polyethylene wax, 2.5 parts of gamma-mercaptopropyltriethoxysilane,
2.5 parts of 2,5- dimethyl -2,5- (di-t-butyl peroxy) hexane, 10 parts of zinc dimethacrylate, N- isopropyls-N '-phenyl
2.5 parts of p-phenylenediamine, 1.5 parts of 2,2,4- trimethyl -1,2- dihyaroquinolines condensate.
In the present embodiment, the Mooney viscosity of the ethylene propylene diene rubber is 57, contents of ethylene 68%, Third monomer
ENB contents are 4.7%.VA contents are 60% in the ethylene-vinyl acetate copolymer.The specific surface area of the white carbon is
200m2/g。
2, a kind of preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, specifically comprises the following steps：
(1) first, according to each component in the present embodiment and its weight ratio, by EP rubbers and based elastomers into
Row is plasticated；Then zinc oxide is added, stearic acid, anti-aging agent, processing aid, white carbon, coupling agent, carbon black, fire retardant, fire-retardant helps
Agent, filler, plasticizer, vulcanizing agent and vulcanization aid, extrusion molding after being kneaded uniformly；
(2) digester (-tor) high temperature and pressure vulcanization, steam pressure 1MPa are carried out to product after molding in step 1)；It vulcanizates
Tubing is clipped, expands simultaneously built-in support tube, you can obtains halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
Embodiment 6
1, a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, the cold shrink tube include the ingredient of following parts by weight：It fills
90 parts of oily ethylene propylene diene rubber, 25 parts of ethylene-vinyl acetate copolymer, 2 parts of zinc oxide, 0.2 part of stearic acid, spray carbon black 30
Part, 30 parts of fume colloidal silica, 30 parts of ammonium polyphosphate, 10 parts of pentaerythrite, 10 parts of melamine, 60 parts of montmorillonite, calcium carbonate
35 parts, 40 parts of paraffin oil, 1 part of polyethylene glycol, 1 part of γ-aminopropyl triethoxysilane, bis- tert-butyl peroxy base -3,3,5- of 1,1-
10 parts of trimethoxy hexamethylene, 0.2 part of triallyltrimelitate, N- isopropyls-N ' -4 parts of diphenyl-para-phenylene diamine.
In the present embodiment, the Mooney viscosity of the oil extended EPDM is 60, contents of ethylene 48%, third list
Body ENB contents are 10%, and oil-filled number is 33 parts.VA contents are 70% in the ethylene-vinyl acetate copolymer.It is described white
The specific surface area of carbon black is 150m2/g。
2, a kind of preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, specifically comprises the following steps：
(1) first, according to each component in the present embodiment and its weight ratio, by EP rubbers and based elastomers into
Row is plasticated；Then zinc oxide is added, stearic acid, anti-aging agent, processing aid, white carbon, coupling agent, carbon black, fire retardant, fire-retardant helps
Agent, filler, plasticizer, vulcanizing agent and vulcanization aid, injection moulding after being kneaded uniformly；
(2) salt bath vulcanization is carried out to product after molding in step 1), curing temperature is 200 DEG C；The tubing warp vulcanizated
It cuts, support tube built in expansion simultaneously, you can obtain halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube.
Comparative example 1
70 parts of bibasic ethylene propylene rubber, 30 parts of ethylene propylene diene rubber, 10 parts of ethylene-vinyl acetate copolymer, zinc oxide 5
Part, 1 part of stearic acid, 50 parts of carbon black N330,10 parts of fume colloidal silica, 60 parts of calcium carbonate, 20 parts of paraffin oil, 5 parts of WB212,
3 parts of vinyltriethoxysilane, 6 parts of cumyl peroxide, 0.2 part of triallylcyanurate, trimethyl -1 2,2,4-,
2 parts of 2- dihyaroquinolines condensate.
Wherein, the Mooney viscosity of the bibasic ethylene propylene rubber is 50, and contents of ethylene 55%, remaining contains for acrylic
Amount；The Mooney viscosity of ethylene propylene diene rubber is 46, contents of ethylene 52%, and third monomer ENB content is 4.3%.The second
VA contents are 70% in alkene-vinyl acetate co-polymer.The specific surface area of the white carbon is 200m2/g。
Comparative example 2
100 parts of oil extended EPDM, 30 parts of ethylene-vinyl acetate copolymer, 5 parts of zinc oxide, 1 part of stearic acid,
35 parts of carbon black N660,25 parts of fume colloidal silica, 60 parts of talcum powder, 8 parts of dibutyl phthalate, 2 parts of polyethylene glycol, second
Bis- 6 parts of (t-butylperoxy diisopropyl) benzene of 5 parts of alkenyl three ('beta '-methoxy ethyoxyl) silane, 1,4-, N, N`- metaphenylenes
2 parts of bismaleimide, N- isopropyls-N ' -2.5 parts of diphenyl-para-phenylene diamine.
Wherein, the Mooney viscosity of the oil extended EPDM is 65, contents of ethylene 66.5%, Third monomer
ENB contents are 4.7%, and oil-filled number is 13 parts.VA contents are 18% in the ethylene-vinyl acetate copolymer.It is described white
The specific surface area of carbon black is 150m2/g。
Comparative example 3
100 parts of ethylene propylene diene rubber, 15 parts of ethylene-vinyl acetate copolymer, 5 parts of zinc oxide, 0.5 part of stearic acid, charcoal
25 parts of black N990,25 parts of precipitated silica, 60 parts of kaolin, 10 parts of dioctyl adipate, 2 parts of WB42, γ-mercapto propyl three
Bis- 6.5 parts of (tert-butyl peroxy base) n-butyl pentanoates of 0.4 part of methyl-monosilane, 4,4-, 2.5 parts of Triallyl isocyanurate, two fourths
2 parts of base aminodithioformic acid nickel.
Wherein, the Mooney viscosity of the ethylene propylene diene rubber is 48, contents of ethylene 64%, third monomer ENB content
It is 8.5%.VA contents are 40% in the ethylene-vinyl acetate copolymer.The specific surface area of the white carbon is 150m2/
g。
Comparative example 4
80 parts of bibasic ethylene propylene rubber, 20 parts of ethylene-vinyl acetate copolymer, 5 parts of zinc oxide, 1 part of stearic acid, carbon black
45 parts of N550,5 parts of precipitated silica, 25 parts of diatomite, 25 parts of paraffin oil, 2 parts of WA48, γ-methacryloxy third
1.8 parts of base trimethoxy silane, 6.5 parts of 2,5- dimethyl -2,5- (di-t-butyl peroxy) -3- hexins, methacrylate
2.5 parts of glycol ester, 2 parts of 2-mercaptobenzimidazole.
Wherein, the Mooney viscosity of the bibasic ethylene propylene rubber is 25, and contents of ethylene 73%, remaining contains for acrylic
Amount.VA contents are 50% in the ethylene-vinyl acetate copolymer.The specific surface area of the white carbon is 50m2/g。
Comparative example 5
85 parts of ethylene propylene diene rubber, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of zinc oxide, 2 parts of stearic acid, carbon black
5 parts of N550,50 parts of fume colloidal silica, 60 parts of calcium carbonate, 8 parts of dioctyl sebacate, 2.5 parts of polyethylene wax, γ-mercapto propyl
2.5 parts of triethoxysilane, 2.5 parts of 2,5- dimethyl -2,5- (di-t-butyl peroxy) hexane, zinc dimethacrylate 10
Part, N- isopropyls-N ' -2.5 parts of diphenyl-para-phenylene diamine, 1.5 parts of 2,2,4- trimethyl -1,2- dihyaroquinolines condensate.
Wherein, the Mooney viscosity of the ethylene propylene diene rubber is 57, contents of ethylene 68%, third monomer ENB content
It is 4.7%.VA contents are 60% in the ethylene-vinyl acetate copolymer.The specific surface area of the white carbon is 200m2/
g。
Comparative example 6
90 parts of oil extended EPDM, 25 parts of ethylene-vinyl acetate copolymer, 2 parts of zinc oxide, 0.2 part of stearic acid,
30 parts of spray carbon black, 30 parts of fume colloidal silica, calcium carbonate 60,40 parts of paraffin oil, 1 part of polyethylene glycol, three second of γ-aminopropyl
1 part of oxysilane, bis- 10 parts of tert-butyl peroxy base -3,3,5- trimethoxies hexamethylenes of 1,1-, 0.2 part of triallyltrimelitate,
N- isopropyls-N ' -4 parts of diphenyl-para-phenylene diamine.
Wherein, the Mooney viscosity of the oil extended EPDM is 60, contents of ethylene 48%, third monomer ENB
Content is 10%, and oil-filled number is 33 parts.VA contents are 70% in the ethylene-vinyl acetate copolymer.The white carbon
Specific surface area be 150m2/g。
Comparative example 1-6：It is corresponding with embodiment 1-6 respectively, difference lies in：Fire retardant is free of in comparative example and fire-retardant is helped
Agent.
Halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube prepared by 1-6 of the embodiment of the present invention obtains following performance：Hardness,
Shao Er A：40-70；Tensile strength, MPa：9-13；Tearing strength, KN/m：25-49；Elongation at break, %：550-900；Volume
Resistivity, Ω cm：1014-1016；Dielectric constant：2.8-3.2；Electrical strength, KV/mm：19-24；Flame retardant rating, UL94V0.
Wherein, in the test of flame retardant property, after carrying out 10 seconds combustion testings twice to sample, flame extinguished at the 3rd second and without appointing
What comburant is fallen down.
The performance of the comparative example 1-6 of the present invention halogen-free flame-retardant environment-friendly EP rubbers cold shrink tubes prepared is tested, is tied
Fruit is：Hardness, Shao Er A：40-65；Tensile strength, MPa：8-11；Tearing strength, KN/m：23-40；Elongation at break, %：
500-800；Volume resistivity, Ω cm：1015-1016；Dielectric constant：2.8-3.2；Electrical strength, KV/mm：19-24, it is fire-retardant
Grade, UL94 V2 are (i.e.：After carrying out 10 seconds combustion testings twice to sample, flame extinguishes in the 27th second, and can ignite
Absorbent cotton below 30cm).
As can be seen that present invention obtains the EP rubbers cold shrink tubes for having both excellent good mechanical property and flame retardant property.
The foregoing is merely the preferred embodiments of the application, are not intended to limit this application, for those skilled in the art
For member, the application can have various modifications and variations.Any modification made by within the spirit and principles of this application,
Equivalent replacement, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube, it is characterised in that：By weight, the cold shrink tube include with
Lower component：
The fire retardant includes：Aluminium hydroxide, magnesium hydroxide, hydrotalcite, melamine cyanurate, hypo-aluminum orthophosphate, tricresyl phosphate
Monooctyl ester, tricresyl phosphate, encapsulated red phosphorus, aluminum diethylphosphinate, expansible graphite, ammonium polyphosphate, pentaerythrite, melamine
It is one or more in amine；
The flame retardant includes：One in zinc borate, mica powder, montmorillonite powder, silicone, attapulgite, vermiculite power, alumina silicate
Kind is a variety of.
2. halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube as described in claim 1, it is characterised in that：The EP rubbers packet
It includes：It is one or more in bibasic ethylene propylene rubber, ethylene propylene diene rubber, oil extended EPDM；Preferably, the third rubber of the second
The Mooney viscosity of glue is 25-65, and contents of ethylene 48%-73%, third monomer ENB content is 0-10%, remaining is propylene
Base content.
3. halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube as described in claim 1, it is characterised in that：The vinyl elastomers
Body is ethylene-vinyl acetate copolymer, wherein vinyl acetate content is between 18%-70%.
4. halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube as described in claim 1, it is characterised in that：The carbon black includes：
It is one or more in N330, N550, N660, N774, N990, spray carbon black；
Preferably, the white carbon includes the mixture of one or both of fume colloidal silica, precipitated silica；
Preferably, the specific surface area of the white carbon is 50-200m2/g；
Preferably, the filler includes one or more in calcium carbonate, talcum powder, kaolin, diatomite.
5. halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube as described in claim 1, it is characterised in that：The plasticizer packet
It includes：Paraffin oil, dioctyl phthalate, dioctyl sebacate, dioctyl adipate, low molecular weight polyisobutene, liquid second
It is one or more in third rubber aromatic oil, naphthenic oil, dibutyl phthalate；
Preferably, the processing aid includes：It is one or more in polyethylene glycol, WB42, polyethylene wax, WA48, WB212；
Preferably, the coupling agent includes：Vinyltriethoxysilane, the vinyltrimethoxysilane, (β-first of vinyl three
Oxygroup ethyoxyl) silane, γ-methacryloxypropyl trimethoxy silane, γ-mercapto oxypropyl trimethyl silane, γ-mercapto third
Ethyl triethoxy silicane alkane, bis- (γ-triethoxysilylpropyl)-tetrasulfides, one kind in gamma-aminopropyl-triethoxy-silane or
It is a variety of.
6. halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube as described in claim 1, it is characterised in that：The vulcanizing agent was
Oxide, including：Bis- (t-butylperoxy diisopropyl) benzene of cumyl peroxide, 1,4-, the bis- (t-butylperoxies of 1,4-
Diisopropyl) benzene, 2,5- dimethyl -2,5- (di-t-butyl peroxy) hexane, 2,5- dimethyl -2,5- (di-t-butyl peroxides
Base) -3- hexins, bis- tert-butyl peroxy base -3,3,5- trimethoxies hexamethylenes of 1,1-, bis- (tert-butyl peroxy base) n-butyl pentanoates of 4,4-
In it is one or more；
Preferably, the vulcanization aid includes：Triallylcyanurate, trihydroxy methyl propane trimethyl acrylate, Sulfur,
Ethyleneglycol dimethyacrylate, N, the bis- furfurylidene-acetones of N`-, N, N`- meta-phenylene bismaleimides, dimethacrylate
It is one or more in zinc, Triallyl isocyanurate, triallyltrimelitate；
Preferably, the anti-aging agent includes：Nickel dibutyl dithiocarbamate, 2,2,4- trimethyl -1,2- dihyaroquinolines
One in condensate, N- isopropyls-N '-diphenyl-para-phenylene diamine, acetone and diphenylamines high-temperature reaction product, 2-mercaptobenzimidazole
Kind is a variety of.
7. the preparation method of halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube as claimed in any one of claims 1 to 6, specific to wrap
Include following steps：
(1) first, according to each component and its weight ratio, EP rubbers and based elastomers are plasticated；Then plus
Enter zinc oxide, stearic acid, anti-aging agent, processing aid, white carbon, coupling agent, carbon black, fire retardant, flame retardant, filler, plasticising
Agent, vulcanizing agent and vulcanization aid are kneaded uniform aftershaping；
(2) product after molding in step 1) is vulcanized, the tubing vulcanizated is clipped, expands simultaneously built-in support tube, i.e.,
Halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube can be obtained.
8. preparation method as claimed in claim 7, it is characterised in that：In step 1), the molding includes：Extrusion molding or note
Penetrate molding；In step 2), the mode of the vulcanization includes：Molding vulcanization, the vulcanization of vulcanization digester (-tor) high temperature and pressure or salt bath vulcanization.
9. low inflaming retarding ethylene propylene rubber cold shrink tube prepared by preparation method as claimed in claim 7 or 8, it is characterised in that：It is described
Low-resistance combustion cold shrink tube includes the component of following parts by weight：80-100 parts of EP rubbers, 10-30 parts of based elastomers, zinc oxide
2-10 parts, 0.2-2 parts of stearic acid, 5-50 parts of carbon black, 5-50 parts of white carbon, 10-150 parts of fire retardant, 15-60 parts of flame retardant,
10-40 parts of filler, 8-40 parts of plasticizer, 1-5 parts of processing aid, 0.4-5 parts of coupling agent, 2.5-10 parts of vulcanizing agent, auxiliary curing agent
0.2-10 parts, 0-4 parts of anti-aging agent；
The EP rubbers cold shrink tube has the following performance：Hardness, Shao Er A：40-70；Tensile strength, MPa：9-13；Tearing is strong
Degree, KN/m：25-49；Elongation at break, %：550-900；Volume resistivity, Ω cm：1014-1016；Dielectric constant：2.8-
3.2；Electrical strength, KV/mm：19-24；Flame retardant rating, UL94V0.
10. halogen-free flame-retardant environment-friendly EP rubbers cold shrink tube as claimed in any one of claims 1 to 6 and/or such as claim 7
Or preparation method described in 8 and/or low inflaming retarding ethylene propylene rubber cold shrink tube as claimed in claim 9, in communication cable, coaxial electrical
Application in cable, medium-low voltage power cable, flame retardant cable.
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Application publication date: 20180928 |