CN101580606B - Cable jacket rubber and preparation method - Google Patents
Cable jacket rubber and preparation method Download PDFInfo
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- CN101580606B CN101580606B CN2009100327633A CN200910032763A CN101580606B CN 101580606 B CN101580606 B CN 101580606B CN 2009100327633 A CN2009100327633 A CN 2009100327633A CN 200910032763 A CN200910032763 A CN 200910032763A CN 101580606 B CN101580606 B CN 101580606B
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Abstract
The invention relates to a cable jacket rubber and a preparation method, wherein the cable jacket rubber has high elastic resilience, softness and abrasive resistance at a low temperature. The cable jacket rubber is characterized in that a base material of the rubber is formed by mixing 30 to 50 weight percent of natural gum and 50 to 70 weight percent of cis-butadiene rubber; a vulcanizing systemin a rubber compounding agent is a low-sulfur high-accelerant vulcanizing system, the addition of sulfur is 0.3 to 0.6 weight percent of that of the base material of the rubbere, the addition of the accelerant tetramethylthiuram disulfide is between 1.0 and 1.3 weight percent, the addition of the accelerant N-cyclohexyl-2-benzothiazole sulfonamide is between 1.8 and 2.2 weight percent, and the addition of the accelerant diphenyl disulfide benzothiazole is between 0.6 and 0.9 weight percent. The cable jacket rubber has wide range of working temperature, and can be bent and distorted randomly without cracking at a long-term usage temperature of between 50 DEG C below zero and 70 DEG C, the impact elasticity is high and can reach 42 percent, the specific elongation is more than 350 percent, and the Akron abrasion loss is less than 2 percent, thus the cable jacket rubber is particularly suitable for wind-power generated electricity tower tube cables.
Description
Technical field
The present invention relates to have high resilience under a kind of low temperature, flexibility, the cable jacket rubber of wear resistance and preparation method are used in particular for connecting wind power station cabin and tower tube cable sheath rubber,
Background technology
Some cable is because of using out of doors, and high especially to anti-environmental requirement, for example aerogenerator is drawn tower tube vertical-rise cable, and use temperature requires to satisfy 65 ℃ to-50 ℃ wide regions, and (for example-50 ℃) is anti-under the low temperature turns round 3000 times and do not ftracture.Existing wind-energy tower tube flexible cable rubber sheath base-material has: natural gum (NR), natural gum+butadiene-styrene rubber binary compound (NR-SBR), chlorinatedpolyethylene (CPE), chloroprene rubber (CR), sulfide type butadiene-acrylonitrile rubber+polyvinyl chloride composite (NBR-PVC), indivedual employing thermoplasticity NBR-PVC mixtures are also arranged, and silicon rubber.Two kinds of rubber of NR and NR-SBR, though still maintain flexibility preferably under the low temperature, elasticity is undesirable at low temperatures, wear resistance is not good yet; Elasticity is very poor under CPE, the CR rubber low temperature, and-30 ℃ harden; The NBR-PVC rubbery intensity is not high, and resistance to low temperature can only reach-40 ℃, and tear strength is poor; Silicon rubber wears no resistance, and intensity has only 1/3 of ordinary rubber.Above rubber all is difficult to really satisfy the service requirements of wind-energy tower tube cable, particularly except that silicon rubber, natural rubber, other rubber are polar polymer, along with temperature decline intermolecular cohesion strengthens, inferior valency power increases very fast, and is stiff to all becoming more than-25 ℃, forfeiture elasticity, cause cable rotation difficulty and produce cracking, thereby be difficult to adapt to below-40 ℃ and more low environment requirement (various rubber performances see Table 1).
Comprehensive each performance of rubber, existing wind-energy tower tube cable sheath, it is more to make sheath with chlorinatedpolyethylene.For example: the disclosed second third insulation wind energy private cable of Chinese patent CN201111984, adopt high strength chlorosulfonated polyethylene compound to make oversheath; The disclosed wind power generation feeder cable of Chinese patent Chinese patent CN201084466 adopts chlorinatedpolyethylene to make sheath; Open low temperature resistant, the anti-crack rubber sleeve flexible cable of used for wind power generation of Chinese patent CN101221836, sheath adopts the chlorinatedpolyethylene base-material, and the cold resisting type softening agent, also is added with 2-5 part Stockholm tar and/or locomotive oil, 3-8 part coupling agent; Thorough poor flexibility, intensity can be influential.Tensile strength 5.5-7.8, elongation 300-510; The disclosed jacket material special for wind energy power generation cable of Chinese patent CN101314661, by 100 parts of polyvinyl chloride (PVC) RESINS, 20～40 parts of sulphur chlorinatedpolyethylenees, 20～40 parts high molten finger ethylene-propylene ester ethyl ester multipolymers mix makes base-material.
In addition, the employing polyurethane jacket is arranged also, as Chinese patent CN201104311 wind energy cable, price height, very poor in processability, moisture resistance gas poor performance.
Though, people know synthetic cis-butadiene cement, have excellent cold property, snappiness and good resistance to abrasion, price is also relatively low, but, cause shrinkability big, the mixing procedure poor performance than other rubber because of its rebound resilience is big, can produce serious roll release phenomenon during batch mixing is difficult to mix, not only be difficult to separately mix, and also be difficult for mixing, mix the inhomogeneous mechanical property variation that causes with other rubber; And be easy to generate incipient scorch in advance, lose processing characteristics.Secondly, self resist this to split poor performance, on cable, use so report successfully.
Substantially unconverted arctic rubber when life-time service and its tensile strength at yield under the disclosed cold condition of Chinese patent CN101333307, tensile yield, hardness and normal temperature.Report has main rubber that the natural gum of employing and cis-butadiene cement and usefulness are arranged, and adds the vulcanizing agent of 1.5-1.8%.This cold gum composition, be mainly rubber plate and develop, the cis-butadiene cement add-on can only reach 30%, can only be used in static cold-resistant goods, can not be applicable to for example cable sheath of dynamically cold-resistant goods, support rubber wear resistance and low temperature elasticity and all can not satisfy cable sheath glue requirement; Secondly, sulfuration reaches 1.5-1.8% greatly with sulfuration dosage, and heat aging property is poor, can cause sulphur to migrate to cable inside, causes copper wire corrosion blackout, and this is that cable institute is unallowed; Besides, it only is to solve the cold-resistant problem of rubber merely, and a lot of mechanical and physical performances do not take into full account, tear strength for example, wear resistance.So be not suitable for cable sheath.Therefore still having is worth improved place.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, and existing high rebound resilience and superior wear resistance under a kind of low temperature are provided, and low-temperature pliability is good, minimum can be not obvious stiff and produce the rimose cable jacket rubbers at-60 ℃ of outdoor temperatures.
Another purpose of the present invention is to provide a kind of above-mentioned cable jacket rubber preparation method.
The present invention's first purpose realizes that main the improvement is to adopt high component cis-butadiene cement to mix with natural gum through test (table 2), takes the low high promotor vulcanization system of sulphur simultaneously, thereby overcomes above-mentioned the deficiencies in the prior art, realizes the object of the invention.Specifically, cable jacket rubber of the present invention comprises rubber base-material and rubber ingredients, it is characterized in that the rubber base-material is mixed with the 50-70wt% cis-butadiene cement by the 30-50wt% natural gum to form; Vulcanization system is in the rubber ingredients: the low high promotor vulcanization system of sulphur, the sulphur add-on is the 0.3-0.6wt% of rubber base-material, accelerant disulfide tetra methylthiuram (TMTD) 1.0～1.3wt%, accelerant N-cyclohexyl-2-[4-morpholinodithio sulphenamide (CZ) 1.8～2.2wt%, accelerant disulfide Dibenzo thiazole (DM) 0.6～0.9wt%.
Other rubber ingredients and consumption among the present invention, to prior art for preparing rubber similar substantially (table 3), the Synergist S-421 95 consumption is all in the rubber base-material.
Vulcanization system of the present invention is made of sulphur, accelerant CZ, TMTD, DM, and it is slow to have an incipient scorch, and vulcanization rate is fast, the state of vulcanization height, and sulphide bond is short, thermotolerance and physical strength height, tearing property is good, does not corrode characteristics such as cable conductor.
In addition, can also add some process modification agent in the rubber combination of the present invention, for example the rosin of rubber base-material 2-3wt% plays and further prevents mixing roll release.
The present invention's second purpose realizes, the cable jacket rubber preparation method, comprise power 1 described batching, it is characterized in that earlier that the natural gum mastication is similar to cis-butadiene cement to Wei Shi plasticity-, it is mixing evenly to add cis-butadiene cement then, add other rubber ingredients again and mix, add vulcanizing agent and promotor at last.
Among the preparation method of the present invention, the natural gum mastication is similar to cis-butadiene cement to Wei Shi plasticity-, mainly be that the applicant gropes to obtain experience, can improve cis-butadiene cement and natural gum mixed performance, eliminate cis-butadiene cement roll release problem, and the shrinkability that reduces rubber.
Cable jacket rubber of the present invention, owing in rubber combination, strengthened the content of cis-butadiene cement, the vulcanization system of the heart and the low high promotor of sulphur of employing, greatly improve the low-temperature performance of gained rubber combination, test gained rubber embrittlement temperature minimum reaching-60 ℃, life-time service temperature-50 ℃～70 ℃, can arbitrarily bend and twist, do not ftracture, satisfy wind-power tower cable service requirements (particularly low temperature anti-turn round requirement) fully, shock elasticity reaches as high as 42%, and Akron abrasion is less than 2%, elongation is greater than 350%, and intensity is greater than 150 kilograms/cm
2, tensile strength 28MPa, unit elongation 725%.Rubber of the present invention is owing to have wide working temperature, good sea water resistance performance and wear resistance, elasticity can be used for wind-power tower cable, outdoor frequent mobile flexible cable, seabed movable type cable, with the naval vessel cable, rubber composition of the present invention can also be used for the travelling belt of requirement wear resistance etc.Rubber combination of the present invention, can be by it be made solution, with two kinds of rubber compositions of the general detection of infrared absorption light, and the detection of property index (especially lower temperature resistance, low temperature elasticity, wear resistance), both separately or jointly can be as differentiating foundation.
Below in conjunction with three specific embodiments; the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as the technical scheme qualification total to the present invention, some do not depart from the unsubstantiality of the present invention's design and change In the view of the technician; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Embodiment
Embodiment: press table 4 embodiment proportioning, natural gum (Wei Shi plasticity-about 0.3) be will purchase earlier and opening rubber mixing machine or Banbury mixer mastication placed, open mastication roll temperature is below 80 ℃, and the Banbury mixer temperature makes the rubber Wei Shi plasticity-of natural gum reach 0.60～0.75 below 100 ℃.The natural gum and the cis-butadiene cement of mastication are dropped in the mixing roll, blend to evenly.Remainder is undertaken by common rubber mixing-milling technique (open technology or close experienced formula technology), for example close experienced technology: the strengthening agent (for example high wear-resistant carbon black (HSCB)) of adding 1/2 and weighting agent are (as lime carbonate earlier, potter's clay, talcum powder etc.), add tenderizer (stearic acid for example, paraffin) mixing 1.5～2.0 minutes, temperature is below 100 ℃, after mixing, add remaining strengthening agent (for example mixed gas carbon black) and weighting agent again, add antioxidant D and promoting agent zinc oxide simultaneously, continued mixing 2.0～3.0 minutes, temperature is below 100 ℃, the sheet cooling down of mixing end back was parked 24 hours, and it is standby to get epoxy glue.Open technology: order of addition(of ingredients) is identical with close experienced technology, constantly playing the triangle bag in reinforced process for example is no less than 4 times, temperature is below 80 ℃, reach and mix, adjust roll spacing 2～4mm, carry out that thin-pass is mixing for example to be no less than 3 times and to reach evenly, cool off mixing ends back sheet down, parked 24 hours, it is standby to get epoxy glue.Add sulphur and promotor before using, turn over the triangle bag more than 3 times mixing evenly, roller temperature is no more than 80 ℃.Add rubber extruding machine, below 60 ℃, head (die head) temperature is carried out cable for 70～80 ℃ and is squeezed rubber and sulfuration at body temperature.
To those skilled in the art; under the present invention conceives enlightenment; some distortion that can directly derive or associate from this patent disclosure; or the substituting of known technology commonly used in the prior art; and the mutual various combination between feature; the for example change of glue furnacing temperature; the change of rubber preparing device; the change of conventional rubber Synergist S-421 95 and consumption; purposes difference or the like; can both realize and basic identical function of the foregoing description and effect, launch for example no longer one by one to describe in detail, all belong to this patent protection domain.
The various rubber performance tables of table 1
| Description of materials | NR | SBR | BR | EPR | CPE | CR | NBR-PVC |
| Bounce-back property | Excellent | Well | Excellent | Excellent | Well | Excellent | Still can |
| Wear-resistant | Excellent | Still can | Well | Still can | Well | Well | Well |
| Low temperature resistant (embrittlement temperature ℃) | -50～-70 | -30～ -60 | -70 | -40～ -50 | -30～ -40 | -35～ -55 | -10 |
| Heat-resisting (the highest use ℃) | 120 | 120 | 120 | 150 | 160 | 130 | 120 |
| Sheath long term operation temperature ℃ | 65～75 | 65～75 | 65～75 | 80～90 | 70～80 | 65～70 | 70～80 |
The compound different ratios physical behavior of table 2 NR-BR binary
Annotate: test shows comprehensive each performance, and cis-butadiene cement is comparatively desirable with 50-70wt%: 30-50wt% with the ratio of natural gum.
Table 3 epoxy glue basis cooperates (wt%)
| Title material | Use level | Title material | Use level |
| NR | 30～50 | Stearic acid | 1.8～2.2 |
| BR | 70～50 | Paraffin | 8～12 |
| Vulcanizing agent TMTD | 1.0～1.3 | Zinc oxide | 7～10 |
| Accelerant CZ | 1.8～2.2 | Talcum powder | 23 |
| Sulphur | 0.3～0.6 | Antioxidant D | 2.3～2.6 |
| High wear-resistant carbon black | 28～32 | Altax | 0.6～0.9 |
| Mixed gas carbon black | 22～18 |
Annotate: various rubber ingredients are the wt% of mixed rubber (NR-BR) base-material.Wherein carbon black, stearic acid, activator zinc oxide, tenderizer paraffin, weighting agent talcum powder, antioxidant D are all similar to the common cable rubber sheath.
Table 4 Example formulations (wt%)
| Form | Example 1 | Example 2 | Example 3 |
| NR | 30 | 40 | 50 |
| BR | 70 | 60 | 50 |
| TMTD | 1.0 | 1.2 | 1.2 |
| CZ | 2.2 | 1.8 | 2.0 |
| High wear-resistant carbon black | 28 | 30 | 32 |
| Mixed gas carbon black | 22 | 20 | 18 |
| Stearic acid | 1.8 | 2.2 | 2.0 |
| Paraffin | |||
| Zinc oxide | 7 | 8 | 8.0 |
| Talcum powder | 23 | 23 | 23 |
| Antioxidant D | 2.3 | 2.5 | 2.6 |
| Sulphur | 0.6 | 0.4 | 0.5 |
| Promotor | 0.9 | 0.6 | 0.8 |
Annotate: except that rubber components, other components are 100% basis with mixed rubber all, add calculating.
Claims (4)
1. cable jacket rubber comprises rubber base-material and rubber ingredients, it is characterized in that the rubber base-material is mixed with the 50-70wt% cis-butadiene cement by the 30-50wt% natural gum to form; Vulcanization system is in the rubber ingredients: the low high promotor vulcanization system of sulphur, the sulphur add-on is the 0.3-0.6wt% of rubber base-material, accelerant disulfide tetra methylthiuram 1.0～1.3wt%, accelerant N-cyclohexyl-2-[4-morpholinodithio sulphenamide 1.8～2.2wt%, accelerant disulfide Dibenzo thiazole 0.6～0.9wt%.
2. according to the described cable jacket rubber of claim 1, it is characterized in that having the rosin of rubber base-material 2-3wt%.
3. cable jacket rubber preparation method, comprise the described batching of claim 1, it is similar to cis-butadiene cement to Wei Shi plasticity-to it is characterized in that earlier natural gum being plasticated, and it is mixing even to add cis-butadiene cement then, add other rubber ingredients again and mix, add vulcanizing agent and promotor at last.
4. according to the described cable jacket rubber preparation method of claim 3, it is characterized in that natural gum plasticates to Wei Shi plasticity-0.60～0.75.
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| CN101580606B true CN101580606B (en) | 2011-08-31 |
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