CN1715319A - Hydrogenized nitrile butadiene rubber and para aromatic polyamide fibre composite material and its preparing method - Google Patents
Hydrogenized nitrile butadiene rubber and para aromatic polyamide fibre composite material and its preparing method Download PDFInfo
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- CN1715319A CN1715319A CN 200410062207 CN200410062207A CN1715319A CN 1715319 A CN1715319 A CN 1715319A CN 200410062207 CN200410062207 CN 200410062207 CN 200410062207 A CN200410062207 A CN 200410062207A CN 1715319 A CN1715319 A CN 1715319A
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Abstract
The composite hydrogenised nitrile-butadiene rubber-para aramatic polyamide fiber material contain hydrogenised nitrile-butadiene rubber 100 weight portions, nanometer white carbon black as reinforcer 30-80 weight portions, para aramatic polyamide fiber 5-30 weight portions, silane as coupling agent 3-8 weight portions, softening plasticizer 6.5-15 weight portions, antiageing agent 2 weight portions, and sulfurizing system 11.5-27.5 weight portions. The hydrogenised nitrile-butadiene rubber has iodine number smaller than 11 mg/100 mg, acrylonitrile content of 35-45 wt% and raw rubber Mooney viscosity at 100 deg.c ML1+4 of 55-85. The para aramatic polyamide fiber is soaked or cut para aramatic polyamide fiber or para aramatic polyamide pulp fiber. Fiber surface treating process is adopted to increase the filled fiber and stuffing amount to make the composite material possess excellent high temperature strength and high temperature oil strength.
Description
It is matrix with the hydrogenated nitrile-butadiene rubber that technical field the present invention relates to a kind of, is furnished with the rubber-base composite material that Nano carbon white, para-aramid fiber are made.Be a kind of extraordinary oil resistant of oil field packing element, resistant to elevated temperatures elastomer material of can be used for.
Background technology is for rubber seal, and the harsh down Working environment of oil well makes that the down-hole sealing is very difficult in the oil drilling, and along with probing develops to deep-well, ultra deep well, the down-hole sealing member must adapt to the work condition environment of harsher complexity.The oil field is in packing element in the environment of high pressure, high temperature and oily medium, also is subjected to the corrosion of hydrogen sulfide, steam, acid simultaneously.Under such Working environment, oil swell, aging, excessively crosslinked isostructural variation take place in elastic composite easily that be used for packing element, cause material hardness to rise, strength degradation, and flexibility decrease, cracking resistance mouth growing ability obviously reduces.The stretch crystallization behavior of base rubber disappearance in elastic composite during high temperature, reasons such as interaction force weakens between filler grain and the base rubber, make the elastic composite degradation, cause packing element to be easy to produce early damage, cause the inefficacy of material.Simultaneously, under the repeated use situation, elastic composite will repeat pressurized, and when pressure was die-offed, elastic composite swelling or dissolved portion gas can expand rapidly, cause elastic composite break inefficacy, just " explosion type decompress(ion) destruction ".Effectively resistance method is hot strength and the high temperature oil intensity that improves elastic composite.
It is the matrix material of base rubber that traditional packing element adopts paracril, but the heat-resistant limit temperature of paracril is 120 ℃, and further intensification is then owing to the high temperature degradation of base rubber causes the mechanical property of matrix material sharply to descend.And the deep-well temperature often reaches more than 150 ℃ at present, so nitile-butadiene rubber composite material can not adapt to the needs of present deep mining.
White carbon black is white amorphous fine powder, and its chemical constitution is: SiO
2NH
2O is widely used as the reinforcing filler of rubber, and its reinforcing effect is only second to carbon black, surpasses other any white strengthening agent.The Si-OH (silanol base) on the surface structure of white carbon black that is surface is exactly because also the white carbon black surface exists active Si-OH group just to make white carbon black have strengthening action.But then cause strong interaction owing to hydrogen bond action between the filler when filling in a large number, make filling-material structureization obvious, produce network effects, increase the hardness of elastomerics rubber unvulcanizate, cause processing difficulties.And the physical action bonding force between filler and rubber can be destroyed in hot environment, thereby produces a large amount of tiny cracks, causes the rapid decline of intensity.
Para-aramid fiber is the industrial fiber of new generation of a kind of high strength, high-modulus, high temperature resistant and resistant to chemical media, is used for modulus and hot strength that elastic composite can significantly improve material.Because the molecular structure of the high-crystallinity of stiff molecule chain formation, high orientation, so para-aramid fiber has the intensity height, distortion is little, modulus is high (dimensional stability is good), chemicals-resistant corrodes and the good characteristics of temperature tolerance.And fibre density is low, is 1.41～1.42Kg.cm
-3, the specific tensile strength height.Have unique high-temperature stability, its second-order transition temperature about 345 ℃, not fusion under the high temperature, percent thermal shrinkage is very little, under 200 ℃, its intensity remains unchanged substantially, therefore can work under 300 ℃ hot environment for a long time.Therefore but its structure has upright and outspoken polymer and high crystallinity, makes its surfactivity low, can't expect to produce high cohesive strength between it and rubber.Aramid fiber dipping cutting staple fibre (DCF) is cut off by macrofiber and forms, smooth surface, and the length homogeneous, since relatively poor with the adhesive property of matrix, therefore need carry out surperficial adhesion process.At " research of aramid fiber short fibre Reinforced Rubber based composites and application present situation " [New Chemical Materials, 1997, ] and " staple fibre strength rubber formula technique " [world rubber industry (12): 7-14,2001,28 (4) 49-58] after the surperficial adhesion process of having reported aramid fiber often adopts precondensation resol and epoxy resin impregnated activation, the method that adopts resorcinol formaldehyde latex adhesive composition (RFL) to handle again, RFL is made up of the initial stage condenses aqueous solution (RF) of Resorcinol and formaldehyde and the mixture of latex (L), at rubber and latex, latex and RF resin, bonding between RF resin and the fiber produces firm bonding strength between the integral body of rubber and fiber.But this adhesion process is at handling macrofiber, and staple fibre is entangled to each other and be difficult to operation in this treating processes, and therefore this treatment process is not suitable for the surface treatment of staple fibre.
Aramid pulp is the surface fibrillation product of aramid fiber, its surperficial fibrillar structure makes it have big specific surface area, therefore the fibrillation product has big surface to contact with rubber, owing to mechanical interlocking has higher bonding strength, this fibrillation has also increased the toughness of fiber, easy fracture not when making it mixing maintains length-to-diameter ratio preferably.But when mixing,, therefore need carry out surface treatment to improve its dispersing property because interfibrous entanglement causes difficulties in dispersion.Reported that at " progress of poly-fibre slurry cake pretreatment " [specialty elastomer goods, 2003,24 (1) 54-56] Dupont and AKZO company have all developed the aramid fiber master batch of rubber with the adhering technique between the Reinforced Rubber fiber.It basic composition is 40% aramid pulp, 40% carbon black and 20% low viscosity polymer.The master batch of this pulp fibers is because the complexity of technology and price are expensive, and the existence of other component has also influenced a large amount of fillings of pulp fibers in the master batch.And can not accomplish the direct filling of fiber, cause the course of processing complexity of rubber unvulcanizate.For then not appearing in the newspapers with white carbon black and coupling agent ppta-pulp fibre surface-treated method.
Summary of the invention the present invention seeks to prepare a kind of special elastomer that is applicable to the oil field packing element.The hydrogenated nitrile-butadiene rubber that employing has excellent over-all properties is a base rubber, cooperation is with the Nano carbon white and the resistant to elevated temperatures para-aramid fiber of big loading level, high temperature resistant in conjunction with base rubber and high-performance fiber, the characteristic of oil resistant and chemical mediator, for improving bond strength and the dispersiveness of fiber in rubber matrix, the big filling that realizes fiber disperses, adopt a kind of fairly simple effective fiber surface-processing method, make fiber and filler have big loading level, thereby make material have special physical and mechanical properties, particularly having excellent hot strength and high temperature oil intensity, is a kind of excellent material that is applicable to preparation oil field packing element.
A kind of hydrogenated nitrile-butadiene rubber of the present invention and para-aramid fiber matrix material is characterized in that: it contains following component and mass fraction: 100 parts of hydrogenated nitrile-butadiene rubbers, 30～80 parts of Nano carbon white tougheners, 5～30 parts of para-aramid fibers, 3～8 parts of silane coupling agents, 6.5～15 parts in softening softening agent, 2 parts in anti-aging agent, 11.5～27.5 parts of vulcanization systems; The iodine number of hydrogenated nitrile-butadiene rubber is less than 11mg/100mg, and vinyl cyanide quality percentage composition is 35～45%, the crude rubber Mooney viscosity ML under 100 ℃
1+455～85; Para-aramid fiber is p-aramid fiber dipping cutting staple fibre or p-aramid fiber pulp fibers.
The specific surface area of the Nano carbon white toughener that the present invention uses is at 120～200m
2/ g, the primary partical diameter is less than or equal to 100nm.
The length specification of the p-aramid fiber dipping cutting staple fibre that the present invention uses is 1mm～6mm.
The silane coupling agent that the present invention uses is γ-methacryloyl propyl trimethoxy silicane or two [3-(triethoxysilyl) propyl group]-tetrasulfide.
The anti-aging agent that the present invention uses is p phenylenediamine type antioxidant and quinoline type antioxidant.
The vulcanization system that the present invention uses is octyl group phenolic resin vulcanization system or halogenation octyl group phenolic resin vulcanization system.
When the present invention adopts the p-aramid fiber pulp fibers to prepare hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material, the preparation method may further comprise the steps, (1) white carbon black and p-aramid fiber pulp fibers are mixed in homogenizer even after, the silane coupling agent that adds with acetone diluted mixes then, in 50～80 ℃ of oven dry down, obtain surface-treated p-aramid fiber pulp fibers in 160～180 ℃ of bakings then; (2) adopt mill, with the mixing rubber unvulcanizate that obtains of resol in the vulcanization leveller in hydrogenated nitrile-butadiene rubber, the vulcanization system and vulcanization accelerator, anti-aging agent, softening agent, surface-treated p-aramid fiber pulp fibers and the vulcanization system; (3) rubber unvulcanizate is 160 ℃ * T at 160 ℃ of following vulcanization curves of beating of temperature by cure conditions
90Following sulfuration is prepared into hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material.
When the present invention adopts p-aramid fiber dipping cutting staple fibre to prepare hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material, the preparation method may further comprise the steps, and (1) cuts the mixing rubber unvulcanizate that obtains of resol in staple fibre and the vulcanization system with the vulcanization leveller in hydrogenated nitrile-butadiene rubber, the vulcanization system and vulcanization accelerator, Nano carbon white toughener, silane coupling agent, softening softening agent, anti-aging agent, p-aramid fiber dipping; (2) rubber unvulcanizate is at 160 ℃ of following vulcanization curves of beating of temperature, and cure conditions is 160 ℃ * T
90Following sulfuration is prepared into hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material.
The hydrogenated nitrile-butadiene rubber and the para-aramid fiber matrix material of the present invention's preparation can be used for preparing the oil field packing element.
Hydrogenated nitrile-butadiene rubber (HNBR) is made by the paracril selective hydrogenation, hydrogenated nitrile-butadiene rubber is when improving heat-resistant aging, anti-sky marquis's property, anti-low-quality fuel oil significantly, tensile strength, the temperature limit of brittleness of sizing material is improved, and is very excellent material of a kind of physical and mechanical properties.The oil-proofness of hydrogenated nitrile-butadiene rubber is better than chloroprene rubber, acrylic elastomer, chlorosulfonated polyethylene rubber, Good Heat-resistance.Along with drilling depth increases, also more and more higher with the requirement of the heatproof of matrix material and oil-proofness to packing element, hydrogenated nitrile-butadiene rubber is owing to have good comprehensive performances.Hydrogenated nitrile-butadiene rubber has good anti-hydrogen sulfide performance in addition, the then not anti-hydrogen sulfide of common paracril.By acid (H
2S) oil field envrionment tests such as environment, anti-amine, oil and steam prove that the field use hydrogenated nitrile-butadiene rubber is had best over-all properties, and have anti-discharge performance high pressure resistant and under high pressure.Therefore, the present invention selects for use hydrogenated nitrile-butadiene rubber as the base rubber of packing element with matrix material.
In order to improve performance of composites, the hydrogenated nitrile-butadiene rubber that the present invention adopts possesses the performance of intensity and oil resistant solvent resistance two aspects, preferably adopts iodine number (mg/100mg) less than 11, and acrylonitrile content is greater than 35%, the mooney viscosity ML of rubber
1+4(100 ℃) hydrogenated nitrile-butadiene rubber 55～85.For example: the product of Doupont company: Zetpol 1010[iodine number (mg/100mg) is 10, acrylonitrile content 44.2%, the mooney viscosity ML of rubber
1+4(100 ℃) are 85]; Zetpol 2010[iodine number (mg/100mg) is 11, acrylonitrile content 36.2%, the mooney viscosity ML of rubber
1+4(100 ℃) are 85] and Zetpol 2010L[iodine number (mg/100mg) be 11, acrylonitrile content 36.2%, the mooney viscosity ML of rubber
1+4(100 ℃) are 57.5] all can satisfy these requirements.
The general structure of organo silane coupling agent can be expressed as YRSiX
3, X is a bonded hydrolysable group on the Siliciumatom in the formula, the most frequently used is alkoxyl group, but also can be chloro base, acetoxyl group etc.When using as coupling agent, X at first hydrolysis forms silanol, and then with inorganic filler surface on hydroxyl reaction.Y system and polymer molecule have the active function groups (as amino, sulfydryl, vinyl, epoxy group(ing), methacryloxy etc.) of avidity or response capacity.Can make two kinds of materials with different properties couplings well by organo silane coupling agent, promptly form the key coat of organic phase-coupling agent-inorganic phase, thereby make matrix material obtain cohesive strength preferably.Act on the white carbon black rubber composite with silane coupling agent, be expected to obtain the chemical bonding effect between filler and the matrix.This chemical bonding effect has the stability under the high temperature, thereby makes elastomerics show as resistance to elevated temperatures preferably.And the enhancing of reactive force between loaded rubber also helps weakening of reactive force between filler grain, thereby helps the dispersion of filler in matrix.
The para-aramid fiber that adopts among the present invention is p-aramid fiber dipping cutting staple fibre or two kinds of fibers of p-aramid fiber pulp fibers.For example: commercially available p-aramid fiber dipping cutting staple fibre (DCF, length is 1mm, 3mm, 6mm) and p-aramid fiber pulp fibers product.
The preparation of hydrogenated nitrile-butadiene rubber of the present invention and para-aramid fiber matrix material, when being p-aramid fiber dipping cutting staple fibre, used para-aramid fiber can adopt conventional Rubber processing technology, when used para-aramid fiber is the p-aramid fiber pulp fibers, the surface treatment that needs the p-aramid fiber pulp fibers to propose by the present invention.
The Nano carbon white that adopts in the composition of matrix material of the present invention requires to have high enhancing ability and high dispersive ability, and specific surface area is at 120～200m
2/ g (BET absorption value), the primary partical diameter is less than or equal to 100nm, belongs to nano-scale white carbon black.For example: the product Ultrasil VN3 of the product 255-N of Nan Ji chemical industrial company and Degussa company.The consumption of white carbon black is high more, and then intensity is high more, but the then networked effect of too much white carbon black is obvious, increases the hardness of rubber unvulcanizate, causes the difficulty of processing.
The adding of coupling agent can not influence the curability of sizing material in the composition of matrix material of the present invention, and has good chemical coupling effect with used silica compound system.The coupling agent that the present invention adopts is a silane coupling agent; for example: γ-methacryloyl propyl trimethoxy silicane [KH570] or two [3-(triethoxysilyl) propyl group]-tetrasulfides [Si-69] etc.; used silane coupling agent must be fit to the resin cure system that adopted
The softening agent that is adopted in the composition of matrix material of the present invention is the tangible polyester softening agent of plasticization effect, not only plastification preferably will be arranged, and handling ease also requires to have high temperature resistant preferably extraction characteristic.For example: the product of first promise company: Santicizer261, Santicizer443, Santicizer438 etc.
Anti-aging agent in the composition of matrix material of the present invention can adopt commercially available rubber anti-aging agent, and using priciple is known.Prevent to have always high temperature resistant preferably extraction characteristic.For example: anti-aging agent is p phenylenediamine type antioxidant (as: N-sec.-propyl-N-diphenyl-para-phenylene diamine [4010NA]) and quinoline type antioxidant (as: 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer [RD] etc.).
The vulcanization system that adopts in the composition of matrix material of the present invention is a phenolic resin vulcanization system.Vulcanization system can be used octyl group phenolic resin vulcanization system or halogenation octyl group phenolic resin vulcanization system.The octyl group phenolic resin vulcanization system comprises vulcanization leveller (as: zinc carbonate, stearic acid), vulcanization accelerator (as tin protochloride etc.) and octyl phenol urea formaldehyde.Halogenation octyl group phenolic resin vulcanization system comprises vulcanization leveller (as: zinc carbonate, stearic acid) and halogenation octyl phenol urea formaldehyde.The using priciple of vulcanization system is known.The vulcanization system consumption is many more, and then cross-linking density is high more.An amount of cross-linking density could produce optimum mechanical properties.
The used mixing facilities of matrix material of the present invention processing be that the rubber of routine is with mill or Banbury mixer.
The p-aramid fiber pulp fibers surface treatment method that the present invention proposes, white carbon black and p-aramid fiber pulp fibers are carried out pre-mixing under low speed in homogenizer, so that the surface interaction of fiber and white carbon black, silane coupling agent with acetone diluted, under high speed, stir so that silane coupling agent at p-aramid fiber pulp and white carbon black surface energy homodisperse, 50 ℃～80 ℃ oven dry down, too high bake out temperature then may cause technologic danger owing to the volatilization of acetone, and baking promptly obtains fluffy pre-treatment p-aramid fiber pulp fibers under high temperature (160 ℃～180 ℃).Single coupled action will take place with white carbon black in silane coupling agent under this storing temperature.Treatment effect as depicted in figs. 1 and 2, Fig. 1 is scanning electronic microscope (SEM) photo of untreated p-aramid fiber pulp fibers, as seen from Figure 1, the p-aramid fiber pulp fibers has the surface of fibrillation, the surface action area of energy increased fiber, but also increased the mutual entanglement effect between the fiber, cause mixing difficulty, and after the surface treatment of p-aramid fiber pulp fibers (as shown in Figure 2), because white carbon black is in a large number attached to fiber surface, energy reduces this entanglement, adds with the base rubber blend just to make man-hour a large amount of fillings of fiber become possibility.Fig. 3 is the SEM photo of the stretching section of not surface treated p-aramid fiber pulp fibers and matrix material, Fig. 4 is the SEM photo of the fibre composite stretching section after the surface treatment, the fiber of matrix material extraction phenomenon is obvious among Fig. 3, and the fiber of Fig. 4 matrix material and base rubber are combined, therefore the fiber after handling has further strengthened the interaction force between fiber and base rubber, and fiber rubber is in conjunction with tightr.
The mechanical property that the matrix material cross-linked rubber of the present invention's preparation reaches is: hardness 88～94 (Shao A); Tensile strength (room temperature) 20.1～34.2Mpa; Tensile strength (160 ℃) 6.9～18.8Mpa; Tear strength (room temperature) 56.1～82.4KN/m; Tear strength (160 ℃) 11.2～22.4KN/m.The matrix material of the present invention's preparation has higher high temperature strength, can satisfy the service requirements of the harsh Working environment of high-temperature packer packing element.The matrix material processing characteristics of the present invention's preparation is good, adopts the conventional compression technology of annotating can successfully make high performance packing element.
Description of drawings
Fig. 1 is the SEM photo of not surface treated p-aramid fiber pulp fibers.
Fig. 2 is the SEM photo with the present invention's employing of the p-aramid fiber pulp fibers after the surface treatment in embodiment 5.
Fig. 3 is the stretching section SEM photo of the matrix material of the not surface treated p-aramid fiber pulp fibers preparation of Comparative Examples 2 usefulness.
Fig. 4 is the stretching section SEM photo of the matrix material of embodiment 3 usefulness surface-treated p-aramid fiber pulp fibers preparation.
Embodiment
The basic recipe of the embodiment of the invention 1～5 is listed in the table 1.The mechanical property of the matrix material of embodiment 1～5 preparation is listed in the table 2, and the mechanical property of the matrix material of Comparative Examples preparation is listed in the table 3.
The preparation method of embodiment 1 and embodiment 2 is as follows:
(1) refining glue: adopt conventional mill, press the basic recipe consumption in the table 1, be docile and obedient preface and add hydrogenated nitrile-butadiene rubber, vulcanization leveller, vulcanization accelerator, softening softening agent, anti-aging agent, silane coupling agent, Nano carbon white toughener, p-aramid fiber dipping cutting staple fibre and the mixing rubber unvulcanizate that obtains of octyl phenol urea formaldehyde successively.
(2) sulfuration: rubber unvulcanizate is at 160 ℃ of following vulcanization curves of beating of temperature, and cure conditions is 160 ℃ * T
90, sulfuration is prepared into hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material.
The preparation method of embodiment 3～5 is as follows:
(1) surface treatment: after low speed in homogenizer is mixed and spares with white carbon black and p-aramid fiber pulp fibers, add the silane coupling agent (silane coupling agent is 1 to 5 with the mass ratio of acetone) of acetone diluted then; High-speed mixing is even again, dries 2 hours down in 80 ℃, obtains surface-treated p-aramid fiber pulp fibers in 10 minutes in 160 ℃ of bakings then.
(2) refining glue: adopt conventional mill, be docile and obedient preface and add hydrogenated nitrile-butadiene rubber, vulcanization leveller, anti-aging agent, softening agent, surface-treated p-aramid fiber pulp fibers, halogenation octyl phenol urea formaldehyde successively, mix and obtain rubber unvulcanizate.
(3) sulfuration: rubber unvulcanizate is at 160 ℃ of following vulcanization curves of beating of temperature, and cure conditions is 160 ℃ * T
90, prepare hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material.
The matrix material of the present invention's preparation is tested normal temperature and high temperature tensile strength according to GB528-82, GB530-81 respectively, normal temperature and high temperature tear strength, hardness etc. are listed in test result in the table 2.
Comparative Examples 1
Adopt DCF (3mm) 25 parts, other prescription and working method are with embodiment 2, and the physicals of the cross-linked rubber of preparation is listed in the table 3, compare with embodiment 2, the DCF of big loading level can not further improve the high-temperature behavior of matrix material, so its use is subjected to certain restriction.
Comparative Examples 2
Adopt the p-aramid fiber pulp fibers, fiber is not carried out surface treatment, other fill a prescription with embodiment 3, adopts the direct blend method identical with embodiment 1 to refine glue, and the physicals of the cross-linked rubber of preparation is listed in the table 3.Compare with embodiment 3, what the present invention's proposition was described has improved the processing characteristics of sizing material greatly to the surface treatment of p-aramid fiber pulp fibers, and makes big loading level p-aramid fiber pulp fibers feasible.The high-temperature behavior of cross-linked rubber, normal temperature performance also improve.
Comparative Examples 3
Bromination octyl phenol urea formaldehyde is with 30 parts in prescription, other prescription and working method are with embodiment 5, compare with embodiment 5 and to learn that the excessive meeting of the consumption of vulcanization system obviously reduces the tear resistance and the high temperature tear resistance of sizing material, and influence other mechanical property of material.
Comparative Examples 4
Do not use the p-aramid fiber pulp fibers in prescription, therefore the p-aramid fiber pulp fibers with in the white carbon black replacement prescription of equivalent needs to add 67.5 parts of white carbon blacks, and other prescription is identical with embodiment 5, adopts direct blend method to refine glue.Owing to there is not the p-aramid fiber pulp fibers, the high-temperature behavior of matrix material particularly high temperature tensile strength reduces greatly.
Comparative Examples 5
In prescription, use the sulfur cross-linking system, other prescription and working method are with embodiment 5, compare with embodiment 5, illustrate that the present invention adopts phenolic resin vulcanization system to have good resistance to elevated temperatures, and sulfur cross-linking system resistance to elevated temperatures is poor, cross-linking density is low, has therefore reduced the resistance to elevated temperatures of material, and other mechanical property also is subjected to certain influence simultaneously.The high temperature degradation of sulfur cross-linking system also makes it can not be used for the packing element of high-temperature work environment.
Table 1
| The basic recipe component | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Hydrogenated nitrile-butadiene rubber | Zetpol 1010 | 100 | 100 | |||
| Zetpol 2010 | 100 | 100 | ||||
| Zetpol 2010L | 100 | |||||
| Nano carbon white | Ultrasil VN3 | 80 | 65 | 50 | ||
| 255-N | 30 | 80 | ||||
| Silane coupling agent | Si-69 | 8 | 6.5 | |||
| KH570 | 3 | 8 | 5 | |||
| Softening softening agent | Santicizer 261 | 10 | ||||
| Santicizer 443 | 6.5 | 15 | 15 | |||
| Santicizer 438 | 15 | |||||
| Anti-aging agent | Anti-RD | 1 | 1 | 1 | 1 | 1 |
| Anti-4010 | 1 | 1 | 1 | 1 | 1 | |
| Vulcanization system | Zinc carbonate | 1 | 1 | 1 | 1 | 1 |
| Stearic acid | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | |
| The octyl group formaldehyde resin | 25 | 15 | 10 | |||
| Bromination octyl group formaldehyde resin | 20 | 15 | ||||
| Tin protochloride | 2 | 2 | 1 | |||
| Para-aramid fiber | DCF(1mm) | 5 | ||||
| DCF(3mm) | 7.5 | |||||
| Ppta-pulp fibre | 30 | 10 | 17.5 |
Table 2
| Physical and mechanical properties | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The performance of 23 ℃ of following sizing materials | ||||||
| Hardness | [Shao A] | 94 | 90 | 93 | 88 | 90 |
| 25% tensile modulus | [MPa] | 8.6 | 9.5 | 34.2 | 15.4 | 27.2 |
| 100% tensile modulus | [MPa] | 14.1 | 15.2 | -- | 21.7 | -- |
| Tensile strength | [MPa] | 23.2 | 20.1 | 34.2 | 21.5 | 30.9 |
| Tensile yield | [％] | 425 | 418 | 25 | 105 | 40 |
| Tensile set | [％] | 54 | 48 | 2 | 6 | 4 |
| Tear strength | [KN/m] | 82.4 | 79.7 | 56.1 | 60.2 | 57.4 |
| The performance of 160 ℃ of following sizing materials | ||||||
| Tensile strength | [MPa] | 6.9 | 8.1 | 18.8 | 14.8 | 1 5.1 |
| Tear strength | [KN/m] | 11.2 | 12.7 | 15.4 | 20.1 | 22.4 |
Table 3
| Physical and mechanical properties | Unit | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | Comparative Examples 5 |
| The performance of 23 ℃ of following sizing materials | ||||||
| Hardness | [Shao A] | 94 | 92 | 90 | 90 | 88 |
| 25% tensile modulus | [MPa] | -- | 27.3 | -- | 3.3 | 27.0 |
| 100% tensile modulus | [MPa] | -- | -- | 4.2 | -- | |
| Tensile strength | [MPa] | 24.1 | 29.4 | 23.4 | 28.4 | 28.6 |
| Tensile yield | [％] | 16 | 50 | 22 | 504 | 45 |
| Tensile set | [％] | 4 | 4 | 2 | 38 | 4 |
| Tear strength | [KN/m] | 83.4 | 58.2 | 36.2 | 71.9 | 55.4 |
| The performance of 160 ℃ of following sizing materials | ||||||
| Tensile strength | [MPa] | 11.9 | 16.2 | 15.2 | 6.0 | 13.5 |
| Tear strength | [KN/m] | 13.5 | 13.5 | 6.1 | 34.2 | 16.9 |
Claims (9)
1, a kind of hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material is characterized in that: it contains following component and quality powder number: 100 parts of hydrogenated nitrile-butadiene rubbers, 30～80 parts of Nano carbon white tougheners, 5～30 parts of para-aramid fibers, 3～8 parts of silane coupling agents, 6.5～15 parts in softening softening agent, 2 parts in anti-aging agent, 11.5～27.5 parts of vulcanization systems; The iodine number of hydrogenated nitrile-butadiene rubber is less than 11mg/100mg, and vinyl cyanide quality percentage composition is 35～45%, the crude rubber Mooney viscosity ML under 100 ℃
1+455～85; Para-aramid fiber is p-aramid fiber dipping cutting staple fibre or p-aramid fiber pulp fibers.
2, matrix material according to claim 1 is characterized in that: the specific surface area of Nano carbon white toughener is at 120～200m
2/ g, the primary partical diameter is less than or equal to 100nm.
3, matrix material according to claim 1 is characterized in that: the length specification of p-aramid fiber dipping cutting staple fibre is 1mm～6mm.
4, matrix material according to claim 1 is characterized in that: silane coupling agent is γ-methacryloyl propyl trimethoxy silicane or two [3-(triethoxysilyl) propyl group]-tetrasulfide.
5, matrix material according to claim 1 is characterized in that: anti-aging agent is p phenylenediamine type antioxidant and quinoline type antioxidant.
6, matrix material according to claim 1 is characterized in that: vulcanization system is octyl group phenolic resin vulcanization system or halogenation octyl group phenolic resin vulcanization system.
7, the preparation method of matrix material according to claim 1, it is characterized in that: the preparation method may further comprise the steps, (1) white carbon black and p-aramid fiber pulp fibers are mixed in homogenizer even after, the silane coupling agent that adds with acetone diluted mixes then, in 50～80 ℃ of oven dry down, obtain surface-treated p-aramid fiber pulp fibers in 160～180 ℃ of bakings then; (2) adopt mill, with the mixing rubber unvulcanizate that obtains of resol in the vulcanization leveller in hydrogenated nitrile-butadiene rubber, the vulcanization system and vulcanization accelerator, anti-aging agent, softening agent, surface-treated p-aramid fiber pulp fibers and the vulcanization system; (3) rubber unvulcanizate is 160 ℃ * T at 160 ℃ of following vulcanization curves of beating of temperature by cure conditions
90Following sulfuration is prepared into hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material.
8, the preparation method of matrix material according to claim 1, it is characterized in that: the preparation method may further comprise the steps, and (1) cuts the mixing rubber unvulcanizate that obtains of resol in staple fibre and the vulcanization system with the vulcanization leveller in hydrogenated nitrile-butadiene rubber, the vulcanization system and vulcanization accelerator, Nano carbon white toughener, silane coupling agent, softening softening agent, anti-aging agent, p-aramid fiber dipping; (2) rubber unvulcanizate is at 160 ℃ of following vulcanization curves of beating of temperature, and cure conditions is 160 ℃ * T
90Following sulfuration is prepared into hydrogenated nitrile-butadiene rubber and para-aramid fiber matrix material.
9, matrix material according to claim 1 is characterized in that: be used to prepare the oil field packing element.
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| CN 200410062207 CN1290915C (en) | 2004-06-30 | 2004-06-30 | Hydrogenized nitrile butadiene rubber and para aromatic polyamide fibre composite material and its preparing method |
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Assignee: Beijing Beihua Xinxiang Technology Development Co., Ltd. Assignor: Beijing University of Chemical Technology Contract fulfillment period: 2008.9.26 to 2014.9.26 Contract record no.: 2008990000813 Denomination of invention: Hydrogenized nitrile butadiene rubber and para aromatic polyamide fibre composite material and its preparing method Granted publication date: 20061220 License type: Exclusive license Record date: 20081016 |
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