CN103599665B - Preparation method of hydrocarbon resin reinforced ultrafine carbon fiber bundles - Google Patents

Abstract

The invention relates to a preparation method of hydrocarbon resin reinforced ultrafine carbon fiber bundles. The preparation method is characterized by comprising the following specific steps: adopting 10 to 15 parts by mass of a thermosetting resin, 81 to 88 parts by mass of a solvent and 2 to 4 parts by mass of a complaisant agent to form an adhesive liquid, after stirring to dissolve, soaking carbon fiber bundles or ropes in the adhesive liquid, after blowing the redundant adhesive liquid with air, placing at the room temperature for 6 to 8 h, then placing in a baking oven with the temperature of 50 to 60 DEG C, and carrying out curing treatment for 2 to 4 h. Strength requirements of the fibers during a carrier preparation process are met, fracture of wires is prevented, the tensile strength is allowed to be slightly increased, at the same time, the bending and flexural resistance performance indexes are increased by 3 to 5 times or more, and the fibers are employed to be used for preparing a particle processed carrier material; and the method has the advantages of ingenious idea, simple process, low cost, easy implementation and the like.

Description

The preparation method of the ultrafine carbon fiber bundle of hydrocarbon resins strengthening

Technical field

The present invention relates to the preparation method of ultrafine carbon fiber bundle of a kind of hydrocarbon resins strengthening, for the preparation of the carrier material of the particle preprocessor of DOC, POC, CSF and similar DPF, also can be applied to the carrier material of SCR postprocessor.

Background technology

For automobile industry, energy-conserving and environment-protective are common issue that Present Global faces; Although the fuel economy of diesel engine is higher than gasoline engine, the discharge capacity due to the particulate of diesel engine is 20 ~ 70 times of gasoline engine, and therefore, the application of diesel engine is subject to certain restrictions;

In the pollutant of automobile, mainly comprise NOX and PM; Discharge quantity of particulate matter all in air, the discharge capacity of motor vehicle occupies the 3rd of total amount, every year close to 600,000 tons;

Motor vehicle granular material discharged in, being mainly distributed in particle size is in the scope of 2.5 ~ 10 μm, and referred to as PM2.5 ~ PM10, this kind of particle to greatly, becomes the emphasis of current motor vehicle exhaust emission purified treatment to the harm of the mankind; Beijing state 5 standard come into effect recently, the discharge quantity of not only stricter restriction PM2.5 ~ PM10, and define the restriction to all particle number PN; Visible, the following post-processing technology for the treatment of PM2.5 ~ PM10 is more general with equipment;

At present, both at home and abroad for the treatment of PM2.5 ~ PM10 is all adopt DPF preprocessor, this technology monopolize by CORNING and NGK company, the factor that expensive price will become restriction and promotes the use of at home, the following problem that also can face more market and use;

DPF is the diesel particulates preprocessor that filter core made by a kind of foamed ceramics, has not through hole that filter area is increased, wall distributed the micropore differed in size in filter core, micropore diameter 8 ~ 16 μm, porosity 40% ~ 50%, channel width 2 ~ 3mm, wall thickness 0.30 ~ 0.45mm; Fresh DPF exemplar can reach 95% to PM treatment effect; After the DPF particulate accumulation used is a certain amount of, rear spray diesel combustion heating, the particulate be deposited on filter core is burnt, and realize regeneration, theoretically, DPF can be permanently effective;

The mechanism of particle filtering is the combination compressing effect, fuel factor and electrical effect; Utilize carrier retaining and colliding particle, and the acting in conjunction of the diffusion of particle self and gravitational settling realizes purification removing; Wherein, compression effect refers to the slightly subflexuose micropore on matrix, and be equivalent to the effect of filter cake and filter bed, being dammed when PM particle is forced through these micropores collects, and reaches filter effect, forms certain thickness filter bed most critical here; Fuel factor refers to and can be understood as isochoric heat effect, and under the particulate of a nanoparticle size is in higher temperature conditions, thermal vibration frequency is accelerated, and the track of Brownian movement is more tortuous, thus, adds the possibility be trapped; And the friction that electrical effect refers in motion between thing and between particle and wall makes it surface with electric charge, though it may have passed macropore above also likely by means of electrostatic interaction retain by the slightly large-sized hole of the next one and elimination;

How to select new material and technique, the macrostructure of the design filter of science and microstructure are important problems;

Possess comparatively filtration efficiency and lower exhaust resistance to the basic demand of particulate filter; The performance of particulate filter affects by many factors such as filter structure parameter and flow parameters, and filter efficiency and exhaust resistance often exist again the trade-off relation of conflicting and mutual restriction; In particular filter structure parameter, particulate filter length, port number, channel width and wall thickness determine length and the area of section of filter, and they not only can have influence on the overall performance of particulate filter; Increase particulate filter length and area of section effectively can improve the filter efficiency of particulate filter and reduce gas-flow resistance, but are subject to the restriction of the installing space of vehicle; Standard specifies that the maximum airflow resistance of the particulate filter of vehicle generally will control at below 10kPa, and in addition, particulate filter also must meet the features such as mechanical strength, thermal stress impact and manufacturing process are easy; Above-mentioned characteristic must rely on carrier new material to realize;

The patent No. is the diesel motor exhaust carbon soot particles catcher/filter patent of CN201020287676.0, in drum housing, be provided with the stainless (steel) wire be closely wound around, described stainless (steel) wire is provided with backfin and belling, but the through duct possessed is unfavorable for the trapping of molecule; The patent No. is the tail gas emission filter patent of CN200920053958.1, it is a concentric tube outsourcing glass, tail gas enters from the side, from the effusion of center afterbody, what play a role in filtering is glass, and this structure exists the problem of air flow method inequality, in addition, the cycle pulse exhaust airstream of automobile engine will dispel glass to be torn, and the life-span is short, loses efficacy very fast; The patent No. is the diesel particulate filter patent of CN200480026612.2, is the DPF ceramic monolith of the wall-flow type of traditional structure; The patent No. is the diesel particulate filter patent of CN200410055292.5, is the DPF Carboround of the wall-flow type that a kind of FBC of employing additive is assisted, and contains the oxide of vanadium, the oxide of tungsten and metal palladium catalyst and finally become CDPF; The patent No. is the honeycomb particulate filters patent of CN01816995.3, be a kind of along flow to axle have different wall as cellular multi-unit structure, be specifically applicable to diesel particulate filter, but it is also applicable to the honeycomb of part stream.Honeycomb thermal capacity gradually changes from arrival end to the port of export; The patent No. is the exhaust gas particle filter of CN200810215253.5 and the process patent of manufacture exhaust gas particle filter, is a kind of exhaust gas particle filter adopting metallic foam support completely; The patent No. is the diesel soot particulate filter device cylinder patent of CN201080028039.4, a kind of diesel soot particulate filter device of woven wire winding of the wall-flow type of many according to certain way arrangement; The patent No. is the diesel exhaust gas purifying filter patent of CN03804171.5, that filling has the particulate ceramic porous body of tridimensional network and forms in filter container, the average grain diameter of described particulate ceramic porous body is 4.0 ~ 20mm, described particulate ceramic porous body has a large amount of artificial pore of being formed therein and to be connected with each other logical intercommunicating pore with adjacent pore, is exposed to the surface of described porous body air cap described in some.

The technical scheme adopted for realizing process particulate matter is not unique, and therefore, the automobile-used particulate matter filter device that exploitation is different from DPF is a technology having very much challenge;

For the PM2.5 ~ PM10 particle disposal standard-required facing the future stricter, some traditional filtering materials, such as, woven wire and metal sintering felt cannot be competent at.

Summary of the invention

The preparation method of the ultrafine carbon fiber bundle that the object of the present invention is to provide a kind of hydrocarbon resins to strengthen, compression effect, fuel factor and electrical effect three kinds of effects are played ultimate attainment, it can prepare the new material of particle processor carrier, after the catalyst of coating oxidized form, the removal effect of PM is maximized; Meeting fiber preparing the requirement of strength in carrier process, preventing fracture of wire, tensile strength is improved slightly, but anti-folding Bending property index improves more than 3 ~ 5 times, adopts this fiber for the preparation of the carrier material of particle process; It is ingenious that the method has thinking, and technique is simple, with low cost, is easy to the features such as realization.

Technical scheme of the present invention is achieved in that the preparation method of the ultrafine carbon fiber bundle that a kind of hydrocarbon resins is strengthened, it is characterized in that concrete steps are as follows: by mass fraction by 10 ~ 15 parts of thermosetting resins, the softener composition binding agent liquid of the solvent of 81 ~ 88 parts and 2 ~ 4 parts, through stirring and dissolving, carbon fiber bundle or rope are dipped in binding agent liquid, after air purges unnecessary binding agent liquid, ambient temperatare puts 6 ~ 8h, then in an oven through 50 ~ 60 DEG C, then through 2 ~ 4h solidification process solidification process.

Described ultrafine carbon fiber bundle is 1K ~ 50K.

Described thermosetting resin is C5 or the C9 Petropols of industry, and solvent is benzinum, and softener is-25# transformer oil.

Good effect of the present invention is the anti-folding and the Bending property that solve fibre bundle, solve and the fracture of wire problem in woven wire ' shuffling ' process, prepared mixed silk netting, be suitable for the carrier material of particle disposal, meet following more harsh automobile emissions standards requirement, be conducive to automobile industry and reduce discharging; There is very high practical value.

Accompanying drawing explanation

Fig. 1 is the schematic diagram before the present invention strengthens.

Fig. 2 is the schematic diagram after the present invention strengthens.

Detailed description of the invention

Below by drawings and Examples, the present invention is further described; embodiment is for illustrate feature of the present invention further; be not equal to restriction the present invention, for the change that those skilled in the art carries out according to the present invention, all should be included within protection scope of the present invention.

embodiment 1

As shown in Figure 2, choose 10 parts of industrial C5 Petropols of industry, add 88 parts of industrial benzinums as solvent, add-25# the transformer oil of 2 parts as softener, stirring and dissolving, form binding agent liquid; Adopt the carbon fiber bundle of commercially available 1K, soak this as binding agent, then, adopt the compressed air of 100Kpa to purge, remove unnecessary binding agent; At room temperature about 25 DEG C, first place 6h, then move on in the baking oven of 50 DEG C, insulation 4h, complete fibre bundle solidification process.

embodiment 2

Choose 13 parts of C5 Petropols of industry, add 84 parts of industrial benzinums as solvent, add-25# the transformer oil of 3 parts as softener, stirring and dissolving, form binding agent liquid; Adopt the carbon fiber bundle of commercially available 1K, soak this as binding agent, then, adopt the compressed air of 100Kpa to purge, remove unnecessary binding agent; At room temperature about 25 DEG C, first place 7h, then move on in the baking oven of 55 DEG C, insulation 3h, complete fibre bundle solidification process.

embodiment 3

Choose 15 parts of C9 Petropols of industry, add 81 parts of industrial benzinums as solvent, add-25# the transformer oil of 4 parts as softener, stirring and dissolving, form binding agent liquid; Adopt the carbon fiber bundle of commercially available 1K, soak this as binding agent, then, adopt the compressed air of 100Kpa to purge, remove unnecessary binding agent; At room temperature about 25 DEG C, first place 8h, then move on in the baking oven of 60 DEG C, insulation 2h, complete fibre bundle solidification process.

embodiment 4

The diameter getting a length 500mm is as shown in Figure 1 the stainless steel tube of 20mm, and two ends are erected, and fixing; Get 1K not through the carbon fiber bundle of adhesive cures process, length 1000mm, the counterweight of one section of fixing upper 100g, the other end is hand-held, rides on stainless steel tube, pulls along the radial 90 degree of directions of stainless steel tube/slides, even if counterweight naturally droops, and then pull along stainless steel tube 90 degree of directions/slide; Move in circles; For the 1K carbon fiber bundle not through adhesive cures process, 3 bouts just find the obvious plucking of fibre bundle, and few fibers breaks; Upper and lower 7 bouts, carbon fiber bundle thoroughly ruptures.

embodiment 5

Carbon fiber bundle in Example 1 after process, repeats the test of embodiment 4,19 bouts, finds fibre bundle plucking, and 28 bout fibre bundles break.

embodiment 6

Carbon fiber bundle in Example 2 after process, repeats the test of embodiment 4,27 bouts, finds fibre bundle plucking, and 39 bout fibre bundles break.

embodiment 7

Carbon fiber bundle in Example 3 after process, repeats the test of embodiment 4,52 bouts, finds fibre bundle plucking, and 77 bout fibre bundles break.

What adopt is the heat-resisting carbon fiber bundle of ultra-fine inorganic, ultra-fine inorganic heat resistance fiber bundle comprises the carbon fiber bundle of 1K ~ 50K, the monofilament normally string diameter of 5 ~ 20 μm, and 1K represents the fibre bundle that 1000 this silks form, in like manner, 50K represents the fibre bundle that 50000 this silks form, carbon fiber is a kind of new material, it possesses the electric conductivity of metalloid, density is equivalent to 1/4 ~ 1/5 of steel, tensile strength after compound is 7 ~ 10 times of steel, reach more than 3000Mpa, although the tensile strength of this new material is very high, but, it is more crisp, shearing resistance, anti-folding and flexing resistance poor, even if this fibre bundle is twisted into ' cord ', still can not change its above-mentioned shortcoming, this limit value it in the application of some occasion, such as, in order to improve the effect of carrier material to the seizure of automobile exhaust particulate, and reduce quality and the cost of carrier, adopt the equipment of the metal fiber wire braided metal silk screen of industry, this carbon fiber bundle and metallic fiber ' mixing hooks and compiles ', composition composite fibre, due to braiding process in fiber will with the metal guiding die plate of braiding apparatus and metal crochet hook carry out comparatively violent mutual folding around and sliding friction, common industrial carbon fiber bundle 100% breaks, the process being woven into ' mesh sheet ' cannot be completed, the present invention adopts the Petropols of 10 ~ 15 parts, the petroleum ether solvent of 81 ~ 88 parts, and-25# industrial transformers the oil of 2 ~ 4 parts, wherein, the Petropols of C5 or C9 specification of industry and petroleum ether solvent and transformer oil can well dissolve mutually, stirring can be made into binding agent liquid, soak this fibre bundle, or fibre bundle is passed from the liquid of above-mentioned binding agent, then, adopt the surface of the dry fibre bundle of wind of room temperature, be wound around rolling, at room temperature place 6 ~ 8h for about 25 DEG C, that unnecessary solvent naturally vapors away, then the baking oven heating 2 ~ 4h of 50 ~ 60 DEG C is put into, make petroleum ether solvent volatilization wherein clean, and transformer oil is not evaporated, trace Petropols just can bond together between fiber filaments and filament, namely solidification and intensive treatment is completed, after fibre bundle solidification and intensive treatment, what pay close attention to is not the raising of tensile strength, but the tolerance of anti-folding in weaving and anti-crawl agentdefiection,

In the present invention, Petropols used are cheap industrial products, hard block body under normal temperature, usually used as the composition of industrial binding agent, and wide material sources; In the present invention, recommendation employing 10 ~ 15 parts of Petropols and 81 ~ 88 parts of petroleum ether solvents at room temperature stir to cause and dissolve each other, the dosage of Petropols is very few, bond effect is poor, equally, the dosage of Petropols is too much, after wire harness process ' really up to the mark ', or ' having fragility ', the requirement that the tolerance that still can not meet anti-folding and anti-crawl agentdefiection is improved; In addition, the present invention specially adds again-25# the transformer oil of 2 ~ 4 parts, can with benzinum and the abundant phased soln of Petropols, flash-point (remaining silent) is greater than 130 DEG C, actual measurement boiling temperature is greater than 160 DEG C, can not vapor away in the curing process, remain in the inside of fibre bundle, make handled fibre bundle keep certain compliance, so that meet the quick continuously bending cabling of 180 degree in braiding process, the addition of transformer oil is very few, cannot improve compliance, but, addition is too much, such as, add more than 10 parts, the bond effect of fibre bundle reduces; In like manner, other mineral oil low viscous also can being selected to replace-25# transformer oil, on the contrary, as adopted full-bodied mineral oil, remaining in ' core ' of fibre bundle, the cleaning difficulty of subsequent handling;

In all industrial binding agents or thermosetting resin, also epoxy resin two component can be adopted as binding agent, such as, adopt the epoxy resin of 5 ~ 8 parts as binding agent, the low molecule amine of 1 ~ 2 part is as curing agent, 1 ~ 3 part of acetone is as diluent, stirring and dissolving is configured to the solution of binding agent, employing diluent is the viscosity in order to adjust binding agent liquid, make it ' core ' that penetrate into fibre bundle rapidly and uniformly, and then complete the immersion of fibre bundle, wind is done, then, at the temperature of 20 ~ 60 DEG C, 2 ~ 6h solidifies process; The shortcoming of this binding agent is adopted to be that the smell of low molecule amine and acetone is larger, after more seriously the fibre bundle of this adhesive treatment completes the braiding of mesh sheet, finishing operations must adopt solvent ' immersion ' mesh sheet, remove the binding agent on fibre bundle, fibre bundle above freely can be distributed at ' grid ' of mesh sheet wiry, give full play to the effect of its filtering PM, obviously, after epoxy resin cure, more difficult employing solvent is deviate from again;

Fibre bundle after method process of the present invention still will ensure certain compliance, if hardness is very high or completely ' rigidity ', be difficult to bending, cannot complete knit operation; In addition, in production, mesh sheet after having woven also will adopt aforesaid solvent wash once, elutes the part or all of binding agent of solidification, does not wash out even still retain a small amount of binding agent, according to the technical process of catalyst, need to sinter at the temperature of 400 ~ 500 DEG C, these ' organically ' binding agent compositions, by carbonization or burning-off, do not affect the performance of catalyst, therefore, some conventional inorganic binders obviously cannot use; And some other organic binding agent also partly can meet this requirement, such as, rosin, tung oil, dystectic wax, natural gum, agar and gelatin etc. also can partly meet the demands.

Claims (2)

1. the preparation method of the ultrafine carbon fiber bundle of a hydrocarbon resins strengthening, it is characterized in that concrete steps are as follows: C5 or the C9 Petropols by mass fraction by 10 ~ 15 parts of thermosetting resins being industry, the solvent of 81 ~ 88 parts is the softener of benzinum and 2 ~ 4 parts is-25# transformer oil composition binding agent liquid, through stirring and dissolving, carbon fiber bundle is dipped in binding agent liquid, after air purges unnecessary binding agent liquid, ambient temperatare puts 6 ~ 8h, then in an oven through 50 ~ 60 DEG C, then through 2 ~ 4h solidification process.

2. the method for the preparation of the ultrafine carbon fiber bundle of hydrocarbon resins strengthening according to claim 1, is characterized in that described ultrafine carbon fiber bundle is 1K ~ 50K.