CN105176090A - Buffer rubber material for electric cable accessory and preparing method thereof - Google Patents

Abstract

The invention discloses a buffer rubber material for an electric cable accessory. The buffer rubber material is prepared from, by weight, 2 parts to 3 parts of diethanol amine, 370 parts to 400 parts of silicone rubber, 50 parts to 60 parts of carbon nanotubes, 80 parts to 90 parts of acrylic acid, 80 parts to 100 parts of dicyclohexyl-carbodiimid, 7 parts to 10 parts of 4-dimethylaminopyridine, 300 parts to 460 parts of tetrahydrofuran, 1.3 parts to 2 parts of silane coupling agents KH550, 120 parts to 150 parts of 65wt%-68wt% vitriol, 100 parts to 130 parts of 95wt%-98wt% nitric acid, 30 parts to 40 parts of ethyl orthosilicate, 2 parts to 3 parts of ammonium hydroxide, 4 parts to 5 parts of sulphur, 4 parts to 6 parts of antiagers AW, 7 parts to 10 parts of triallyl isocyanurate, 5 parts to 9 parts of rosin, 10 parts to 13 parts of dihydrate gypsum powder and 10 parts to 16 parts of polyisoprene. The buffer rubber material for the electric cable accessory is good in surface flexibility, high in shock strength, good in rebound resilience, quite good in buffering effect and high in electric-cable-accessory protectiveness.

Description

A kind of cable accessory yielding rubber material and preparation method thereof

Technical field

The present invention relates to field of cable technology, particularly relate to a kind of cable accessory yielding rubber material and preparation method thereof.

Background technology

Because carbon nanotube can improve the mechanical property of matrix material, electrical property and other performances, so carbon nanotube/rubber composite causes increasing concern.In order to realize the object strengthened, two problems is had to need to solve: one is the scattering problem of carbon nanotube, another is that the interface problem of carbon nanotube and matrix compares inertia due to carbon nano tube surface, and specific surface area compares great Yi and causes reunion, so the effect of carbon nanotubes reinforced polymer is not clearly " based on this reason, a lot of people starts to carry out physical or chemical treatment to carbon nanotube, in the middle of these methods, the method that acid treatment produces oxy radical is that one is conventional and efficient, because it can provide effectively/reflecting point, thus realize chemical bond with matrix resin and be connected " but, in most cases, the group that this method produces is often little, enough connections and matrix bonding can not be provided " so, in order to increasing of realization response point, just need to introduce more functional group, come and matrix resin effect.

Summary of the invention

The object of the invention is exactly the defect in order to make up prior art, provides a kind of cable accessory yielding rubber material and preparation method thereof.

The present invention is achieved by the following technical solutions:

A kind of cable accessory yielding rubber material, it is made up of the raw material of following weight parts:

Diethanolamine 2-3, silicon rubber 370-400, carbon nanotube 50-60, vinylformic acid 80-90, N, nitric acid 100-130, the tetraethoxy 30-40 of sulfuric acid 120-150,95-98wt% of N'-Dicyclohexylcarbodiimide 80-100, DMAP 7-10, tetrahydrofuran (THF) 300-460, Silane coupling agent KH550 1.3-2,65-68wt%, ammoniacal liquor 2-3, sulphur 4-5, antioxidant A W4-6, cyanacrylate 7-10, rosin 5-9, dihydrate gypsum powder 10-13, polyisoprene 10-16.

A preparation method for described cable accessory yielding rubber material, comprises the following steps:

(1) above-mentioned rosin is joined in 6-8 dehydrated alcohol doubly, insulated and stirred 10-13 minute at 60-70 DEG C, add polyisoprene, send in the oil bath of 120-130 DEG C, insulated and stirred 6-10 minute, discharging, adds the 5-7% of above-mentioned silicon rubber weight while hot, be stirred to normal temperature, obtain Abietyl modified rubber;

(2) get the 60-70% of above-mentioned cyanacrylate weight, join in 2-3 dehydrated alcohol doubly, stir, add the 10-15% of above-mentioned Abietyl modified rubber weight, 100-200 rev/min is stirred 30-40 minute, obtains pre-mixed alcoholic liquid;

(3) sulfuric acid of above-mentioned 65-68wt%, the nitric acid mixing of 95-98wt%, stir, add carbon nanotube, ultrasonic agitation 20-24 hour, condensing reflux 50-60 minute at 120-140 DEG C, suction filtration, washing, dry, obtain acidifying carbon nanotube;

(4) by above-mentioned acidifying carbon nanotube, vinylformic acid, N, N'-Dicyclohexylcarbodiimide, tetrahydrofuran (THF), DMAP mix, ultrasonic 20-30 minute, raised temperature is 60-65 DEG C, drips above-mentioned Silane coupling agent KH550, under nitrogen protection, magnetic agitation 46-50 hour, suction filtration, vacuum-drying, obtains silane-modified carbon nanotube;

(5) remaining Abietyl modified rubber is mixed with diethanolamine, dihydrate gypsum powder, insulated and stirred 1-2 hour at 50-60 DEG C, suction filtration, vacuum-drying, obtain rubber stone flour;

(6) above-mentioned silane-modified carbon nanotube is joined in 100-120 times of deionized water, ultrasonic agitation 1-2 hour, add tetraethoxy, ammoniacal liquor, pre-mixed alcoholic liquid, insulation reaction 4-6 hour at 50-60 DEG C, suction filtration, washing, vacuum-drying, mix with above-mentioned rubber stone flour, ball milling is even, obtains carbon silicon hybridization matrix material;

(7) mixed with each raw material except sulphur by above-mentioned carbon silicon hybridization matrix material, send into mill mixing even, rubber unvulcanizate is carried out thin-pass, adds sulphur, compression molding on vulcanizing press, curing temperature is 168-170 DEG C.

Advantage of the present invention is:

Reaction mechanism of the present invention is:

Acrylic acid oligomer has arrived acidifying carbon nano tube surface by acetify reactive grafting, and acrylic acid reaction being introduced as next step provides a large amount of carboxyl reaction points, and numerous carboxylic groups can improve the dispersiveness of functionalized carbon nanotubes simultaneously; Then carboxyl can be easy to react with Silane coupling agent KH550, is transformed into siloxanes, is finally hydrolyzed to silica alcohol radical in the basic conditions again; Under alkaline environment, with silica alcohol radical for reflecting point, by the hydrolysis of positive silicic acid second vinegar, generate silica dioxide granule at functionalized carbon nanotubes surface in situ.

CABLE MATERIALS of the present invention has very high tensile strength and hardness, be due to:

(1) between carbon nanotube and the macromolecular chain of silicon rubber by opening refining effect, being mutually wound three-dimensional network structure;

(2) because silica modified carbon nano tube surface has silica dioxide granule, make the surface irregularity of pipe, when carbon nanometer tube/silicon rubber composite carries out stressed, the slippage between carbon nanotube and macromolecular chain becomes more difficult, is conducive to the raising of mechanical property;

(3) silica modified carbon nano tube surface contains a large amount of silicone hydroxyl, they can and the main chain of silicon rubber between there is hydrogen bond action, make the interface interaction between silica modified carbon nanotube and silicon rubber more firm.

Cable accessory yielding rubber material surface of the present invention snappiness is good, excellent in cushion effect, and rebound resilience is good, has good buffering effect, strong to the protectiveness of cable accessory.

Embodiment

A kind of cable accessory yielding rubber material, it is made up of the raw material of following weight parts:

Diethanolamine 2, silicon rubber 370, carbon nanotube 50, vinylformic acid 80, N, N' Dicyclohexylcarbodiimide 80,4 Dimethylamino pyridine 7, tetrahydrofuran (THF) 300, Silane coupling agent KH550 1.3, the sulfuric acid 120 of 65wt%, the nitric acid 100 of 95wt%, tetraethoxy 30, ammoniacal liquor 2, sulphur 4, antioxidant A W4, cyanacrylate 7, rosin 5, dihydrate gypsum powder 10, polyisoprene 10.

A preparation method for described cable accessory yielding rubber material, comprises the following steps:

(1) joined by above-mentioned rosin in the dehydrated alcohol of 6 times, at 60 DEG C, insulated and stirred 10 minutes, adds polyisoprene, send in the oil bath of 120 DEG C, insulated and stirred 6 minutes, discharging, add 5% of above-mentioned silicon rubber weight while hot, be stirred to normal temperature, obtain Abietyl modified rubber;

(2) get 60% of above-mentioned cyanacrylate weight, join in the dehydrated alcohol of 2 times, stir, 10%, 100 revs/min that add above-mentioned Abietyl modified rubber weight are stirred 30 minutes, obtain pre-mixed alcoholic liquid;

(3) sulfuric acid of above-mentioned 65wt%, the nitric acid mixing of 95wt%, stir, add carbon nanotube, ultrasonic agitation 20 hours, condensing reflux 50 minutes at 120 DEG C, suction filtration, washing, dry, obtain acidifying carbon nanotube;

(4) by above-mentioned acidifying carbon nanotube, vinylformic acid, N, N' Dicyclohexylcarbodiimide, tetrahydrofuran (THF), 4 Dimethylamino pyridine mixing, ultrasonic 20 minutes, raised temperature is 60 DEG C, drips above-mentioned Silane coupling agent KH550, under nitrogen protection, magnetic agitation 46 hours, suction filtration, vacuum-drying, obtains silane-modified carbon nanotube;

(5) mixed with diethanolamine, dihydrate gypsum powder by remaining Abietyl modified rubber, insulated and stirred 1 hour at 50 DEG C, suction filtration, vacuum-drying, obtains rubber stone flour;

(6) above-mentioned silane-modified carbon nanotube is joined in 100 times of deionized waters, ultrasonic agitation 1 hour, add tetraethoxy, ammoniacal liquor, pre-mixed alcoholic liquid, insulation reaction 4 hours at 50 DEG C, suction filtration, washing, vacuum-drying, mix with above-mentioned rubber stone flour, ball milling is even, obtains carbon silicon hybridization matrix material;

(7) mixed with each raw material except sulphur by above-mentioned carbon silicon hybridization matrix material, send into mill mixing even, rubber unvulcanizate is carried out thin-pass, adds sulphur, compression molding on vulcanizing press, curing temperature is 168 DEG C.

Performance test:

Elongation at break: 533%;

Tensile strength: 7.6N/mm2;

Aging rear tensile strength retention rate (120 DEG C, 170h): 75%;

Aging rear extension at break retention rate (120 DEG C, 170h): 80%.

Claims (2)

1. a cable accessory yielding rubber material, is characterized in that what it was made up of the raw material of following weight parts:

Diethanolamine 2-3, silicon rubber 370-400, carbon nanotube 50-60, vinylformic acid 80-90, N, nitric acid 100-130, the tetraethoxy 30-40 of sulfuric acid 120-150,95-98wt% of N'-Dicyclohexylcarbodiimide 80-100, DMAP 7-10, tetrahydrofuran (THF) 300-460, Silane coupling agent KH550 1.3-2,65-68wt%, ammoniacal liquor 2-3, sulphur 4-5, antioxidant A W4-6, cyanacrylate 7-10, rosin 5-9, dihydrate gypsum powder 10-13, polyisoprene 10-16.

2. a preparation method for cable accessory yielding rubber material as claimed in claim 1, is characterized in that comprising the following steps:

(1) above-mentioned rosin is joined in 6-8 dehydrated alcohol doubly, insulated and stirred 10-13 minute at 60-70 DEG C, add polyisoprene, send in the oil bath of 120-130 DEG C, insulated and stirred 6-10 minute, discharging, adds the 5-7% of above-mentioned silicon rubber weight while hot, be stirred to normal temperature, obtain Abietyl modified rubber;

(2) get the 60-70% of above-mentioned cyanacrylate weight, join in 2-3 dehydrated alcohol doubly, stir, add the 10-15% of above-mentioned Abietyl modified rubber weight, 100-200 rev/min is stirred 30-40 minute, obtains pre-mixed alcoholic liquid;

(3) sulfuric acid of above-mentioned 65-68wt%, the nitric acid mixing of 95-98wt%, stir, add carbon nanotube, ultrasonic agitation 20-24 hour, condensing reflux 50-60 minute at 120-140 DEG C, suction filtration, washing, dry, obtain acidifying carbon nanotube;

(4) by above-mentioned acidifying carbon nanotube, vinylformic acid, N, N'-Dicyclohexylcarbodiimide, tetrahydrofuran (THF), DMAP mix, ultrasonic 20-30 minute, raised temperature is 60-65 DEG C, drips above-mentioned Silane coupling agent KH550, under nitrogen protection, magnetic agitation 46-50 hour, suction filtration, vacuum-drying, obtains silane-modified carbon nanotube;

(5) remaining Abietyl modified rubber is mixed with diethanolamine, dihydrate gypsum powder, insulated and stirred 1-2 hour at 50-60 DEG C, suction filtration, vacuum-drying, obtain rubber stone flour;

(6) above-mentioned silane-modified carbon nanotube is joined in 100-120 times of deionized water, ultrasonic agitation 1-2 hour, add tetraethoxy, ammoniacal liquor, pre-mixed alcoholic liquid, insulation reaction 4-6 hour at 50-60 DEG C, suction filtration, washing, vacuum-drying, mix with above-mentioned rubber stone flour, ball milling is even, obtains carbon silicon hybridization matrix material;

(7) mixed with each raw material except sulphur by above-mentioned carbon silicon hybridization matrix material, send into mill mixing even, rubber unvulcanizate is carried out thin-pass, adds sulphur, compression molding on vulcanizing press, curing temperature is 168-170 DEG C.