CN108895216A - A kind of hose - Google Patents

A kind of hose Download PDF

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Publication number
CN108895216A
CN108895216A CN201810802931.1A CN201810802931A CN108895216A CN 108895216 A CN108895216 A CN 108895216A CN 201810802931 A CN201810802931 A CN 201810802931A CN 108895216 A CN108895216 A CN 108895216A
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China
Prior art keywords
parts
layer
rubber
polypropylene
inner lining
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CN201810802931.1A
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Chinese (zh)
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不公告发明人
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Tianjin Zhongtian Jingke Technology Co Ltd
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Tianjin Zhongtian Jingke Technology Co Ltd
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Priority to CN201810802931.1A priority Critical patent/CN108895216A/en
Publication of CN108895216A publication Critical patent/CN108895216A/en
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00Hoses, i.e. flexible pipes
    • F16L11/04Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/08Hoses, i.e. flexible pipes made of rubber or flexible plastics with reinforcements embedded in the wall
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06Unsaturated polyesters
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/16Applications used for films
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/068Ultra high molecular weight polyethylene

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

The invention discloses a kind of hoses,With linear low density polyethylene (LLDPE),Ultra-high molecular weight polyethylene and high molecular crosslink polyethylene are primary raw material,Science compounding prepares inner lining film with the chemical substance with good adhesion performance after rubber tube vulcanization,Sided corona treatment is carried out to inner lining film adhesive surface and rubber tube adhesive surface simultaneously,And the glass steel reinforcing fiber with shielding property is compounded in superficial layer,So that rubber tube superficial layer has excellent anti-radiation performance,Conveyance conduit is solved because of ionising radiation bring security risk,A kind of inner lining film is finally prepared to be firmly bonded,Anti-radiation performance is strong,It can transport LPG,LNG and strong corrosive chemical solvent hose,It is to X in nuclear radiation,The absorptivity of gamma-rays and various neutrons may be up to 97.5-99.5%,Inner lining film and the bonding force (N/25mm) of rubber layer reach 160-180.

Description

A kind of hose
The application is divisional application, original application application number:201510590822.4 the applying date:2015.09.16, invention name Claim:A kind of hose and preparation method thereof.
Technical field
The present invention relates to rubber tube, in particular to a kind of hose and preparation method thereof.
Background technique
The rubber tube in China passes through development in more than 50 years with industry, plays to national economy indispensable with interplanting With raising and new diseases especially with China's Mechanization Level, rubber tube band industry is constantly and related fields It interpenetrates, has opened up application range and the field of rubber tube band, product is widely used in coal, metallurgy, cement, harbour, mine The fields such as mountain, petroleum, automobile, weaving, light industry, engineering machinery, building, ocean, agricultural, Aeronautics and Astronautics.In recent years, rubber tube Band industry, kind, specification, the quality of product have obtained lasting, quick, coordination, the development of health, have substantially met domestic market Demand, improve the competitiveness in the international market of product.
Currently, China has become the production of world's rubber tube band and consumption big country.Whole nation rubber tube band of certain scale Manufacturing enterprise 812.It is counted according to glue tube belt branch of rubber industry association, the annual output of whole nation conveyer belt reaches 3.6 hundred million at present m2, V band yield reach 2,100,000,000 Am, sebific duct yield ranks world's anteposition up to 6.6 hundred million Bm, product yield.2010, China rubber Sebific duct band manufacturing income scale is up to 223.62 hundred million yuan.At the same time, since Eleventh Five-Year Plan, China's rubber tube band industry profession Research and development be constantly progressive, not only existing rubber tube band is improved in terms of sizing material, technique, performance and cost, It is allowed to constantly meet user's requirement and adapts to market needs, and continually develop new product and new technology, fill the domestic gaps, perhaps The multinational performance for producing glue tube belt has been approached or reaches advanced world standards, this further squeezes into the international market wound for home products Condition is made.The industrial expansions such as coal, steel, cement, harbour, mine, petroleum, automobile, weaving, light industry, machinery will give rubber Sebific duct brings good opportunity with the development of industry, it is contemplated that rubber tube band manufacturing marketing scale is up to 36,000,000,000 within 2015 Member.
Production method has a molding and steam vulcanization (cure) method, and product characteristic is rubber tube series of products, have oil resistant, acid and alkali-resistance, The conveying of the characteristics such as heat-resisting, pressure-resistant and attraction rubber tube.Most of rubber tubes have nontoxic, environmentally friendly but some more demanding Oil/Gas Pipe is added to fire retardant in rubber material, can generate slightly containing poisonous and harmful substance to human body and atmosphere in fire retardant It influences.The characteristic of rubber tube is also;Physiological inertia, UV resistant, resistance to ozone, high-low temperature resistant (- 80 to 300 degree), transparency be high, Screen resilience is strong, the performances such as the permanent shape of compression resistant, oil resistant, stamping resistance, acid and alkali-resistance, wear-resisting, fire retardant, proof voltage, conduction.Its material There are many types, such as NBR nitrile rubber to be widely used in brake vacuum pipe according to the difference of processing technology for material, and oil resistivity contains glue well Amount is high, but resistance to ozone is relatively poor;EPDM ethylene propylene diene rubber is for automobile water pipe series, such as radiator rubber hose, air-conditioner pipe. There are also the higher materials of some performances, such as AEM acrylic ester high-temperature.Every kind of rubber has its characteristic, therefore in glue It is particularly important above pipe the selection of material.The substantially material that uses of high-grade car is relatively preferable, and vehicle, a minibus slightly uses Material is poor, and such as one, there are also using nitrile rubber, as fuel pipe, nitrile rubber is not suitable for fuel oil to vehicle at present at present slightly System, and the chlorohydrin rubber fluorine sebific duct substituted is applied than wide.
The rubber tube product having disclosed and preparation method thereof is more:Application No. is 201220320377.1 Chinese patents A kind of novel hydraulic oil transportation rubber tube is disclosed, it is specially a kind of that there is antistatic, high-low temperature resistant and ageing-resistant, corrosion-resistant, resistance Fire the rubber petroleum pipeline of environmental protection.Petroleum pipeline structure includes superficial layer, middle layer and three layers of internal layer.Superficial layer by with antistatic, The good ethylene propylene diene rubber of high-low temperature resistant, ageing-resistant performance and fabrics of polyester are combined, and middle layer is with fire-retardant The bibasic ethylene propylene rubber of function is combined with braided steel wire, and internal layer is made of the nitrile rubber with good oil resistance.It is defeated Oil pipe has good oil resistivity, resistant of high or low temperature, ageing-resistant performance, can prolong the service life and rubber tube structure is simple, mechanics Performance is good, low in cost.Application No. is 201510049105.0 Chinese patents to disclose a kind of heat-and corrosion-resistant rubber tube, relates to And sebific duct manufacturing technology field, it include rubber tube body, the rubber tube body includes the interior rubber set gradually from inside to outside Glue-line, casing ply, middle rubber layer, coppered steel wire braiding layer and outer rubber layer, the inner rubber layer are fluororubber layer, the middle rubber Glue-line and the outer rubber layer are butadiene-styrene rubber layer;The inner rubber layer, the casing ply, the middle rubber layer, the plating Copper steel wire braid and the outer rubber layer vulcanization connection, compared with prior art, heat-and corrosion-resistant rubber tube of the present invention it is resistance to Hot and corrosion resistance increases substantially, and meets the needs that conveying has certain corrosive high-temperature gas or liquid.Application number For
201310635893.2 Chinese patent disclose a kind of anti-corrosive rubber tube material, which is characterized in that raw material is each Component forms as follows according to parts by weight:30-40 parts of EP rubbers, 25-30 parts of solution polymerized butadiene styrene rubber, SRR-16 reclaimed rubber 15-20 Part, 1-2 parts of benzoyl peroxide, 3-4 parts of NXT silane coupling agent, 4-7 parts of nano-graphite, 7-9 parts of paraffin, talcum 3-4 powder, oxygen Change zinc 0.7-0.9 parts, 0.6-0.8 parts of zinc stearate, 2-4 parts of epoxy resin, the bis- thiosulfuric acid disodiums of hexa-methylene -1,6- 0.7-0.9 parts, 1.5-1.8 parts of titanium dioxide, 1-3 parts of white oil, AT-100.3-0.5 parts of antioxidant, butylated hydroxytoluene 0.8 Part, 2-4 parts of sulphur.Hose material obtained has preferable resistance to various polar chemical product such as acid, alkali, oxidant, Non-aging, low raw-material cost, excellent product performance have a extensive future.Application No. is 200810224959.8 China Patent discloses a kind of preparation method of carbon nanotube-natural rubber compound material, it is characterised in that with epoxy natural rubber As the compatilizer between carbon nanotube and natural rubber, using excellent compatible between epoxy natural rubber and natural rubber Property and the chemical reaction between epoxy natural rubber and carbon nanotube, improve dispersion of the carbon nanotube in natural rubber Effect enhances the interaction between carbon nanotube and natural rubber, prepares high-performance carbon nanotube-natural rubber composite wood Material;The stretching of the sulfide film of the composite material
Intensity is 26~30MPa, and elongation rate of tensile failure is 750~900%, and 300% stress at definite elongation is 4.0~6.0MPa.On Disclosed patent is stated mainly to be changed from performances such as corrosion-resistant, ageing-resistant, resistance to temperature, acid and alkali-resistance, anti-flammability, mechanical strengths Into, consider that erosion resistant coating falls off the also less of problem, yet there are no the relevant report of related radiation-proof rubber pipe, this for transfer oil and The pipeline of natural gas brings major safety risks.
But for corrosion resistant rubber tube, inner wall section is corrosion-resistant key with macromolecular lining film, and domestic technique is very Difficulty reaches inner lining film and closely connect with sebific duct body, is easy to fall off.Application No. is 201180075440.8 Chinese patents to disclose A kind of resin layer and the outstanding rubber/plastics composite soft tube of the adhesiveness of rubber layer, as solution, which provides one kind Rubber/plastics composite soft tube, has inner tube, and said inner tube has the resin layer as innermost layer and has adjacent with the innermost layer The rubber layer connect, the material that the resin layer uses are the resin combination containing resin, and the resin, which at least contains, has carboxylic The ionomer of acid metal salt, the material that the rubber layer uses are the rubber composition containing rubber, and the rubber at least contains Epoxidezed rubber.This application inventor etc. thinks it may be due to carboxylic acid metal why resin layer can bond with rubber layer Salt is reacted with epoxy group possessed by epoxidezed rubber.Function of the rubber tube of the patent disclosure also without radiation protection Property, the caking property of resin layer and rubber layer is not still highly desirable.
Therefore, how to be made that macromolecular lining film erosion resistant coating caking property is excellent, and can transport with good radiativity The hose of LPG, LNG and strong corrosive chemical solvent is the unremitting pursuit of those skilled in the art.
Summary of the invention
Technical problem solved by the invention is to overcome the defect of existing anti-corrosive rubber pipe, with low density polyethylene (LDPE) (LLDPE), ultra-high molecular weight polyethylene (UHMWPE) and high molecular crosslink polyethylene are primary raw material, science compounding and rubber tube With polyimides, tetraethylenepentamine, alpha-sulfo-fatty acid alkyl ester salt, epoxy resin, the SBR of good adhesion performance after vulcanization The chemical substances such as latex, rosin prepare inner lining film, carry out at corona using while to inner lining film adhesive surface and rubber tube adhesive surface The method of reason to enhance its caking property, and is compounded with the glass steel reinforcing fiber with shielding property in superficial layer, so that Rubber tube superficial layer has excellent anti-radiation performance, especially solves the pipeline of transfer oil and natural gas because ionising radiation is brought Security risk, finally prepare a kind of inner lining film and be firmly bonded, anti-radiation performance is strong, can transport LPG, LNG and strong corrosive chemistry The hose of solvent.
In order to achieve the above object, the present invention uses following technical scheme:
A kind of hose, including rubber tube body, the rubber tube body successively include internal layer, middle layer and table from inside to outside Surface layer;
The internal layer is oil resistant, anti-corrosion layer;
The middle layer is fire-retardant, enhancement layer;
The superficial layer is antistatic, radiation protective layer;
Further, the internal layer is by ethylene-propylene-diene monomer glue-line and the inner lining film with good adhesion performance is at least through sulphur Change bonds;
The ethylene propylene diene rubber color is milky;
The material for preparing of the inner lining film mainly includes linear low density of polyethylene (LLDPE), ultra-high molecular weight polyethylene (UHMWPE) one or more and in high molecular crosslink polyethylene, inner lining film is with a thickness of 0.35-0.5mm;
Preferably, the inner lining film is mainly prepared by the raw material of following parts by weight:20-40 parts of LLDPE, polyvinyl alcohol 20-30 parts, 15-25 parts of UHMWPE, 10-20 parts of high molecular crosslink polyethylene, 8-10 parts of polyimides, tetraethylenepentamine 5-8 Part, 5-7 parts of alpha-sulfo-fatty acid alkyl ester salt, 5-7 parts of epoxy resin, 7-9 parts of SBR latex, 6-8 parts of rosin;
Blow molding, stretching film forming after the inner lining film is squeezed out raw material using conventional method.
Further, the middle layer by ethylene propylene diene rubber and EPDM cord fabric thread, polypropylene enhancing composite material, Fire retardant, brass-plated steel wire braiding are combined;It is preferred that vulcanization bonding;
Polypropylene of the middle layer at least containing its quality 5-30% enhances composite material;
Preferably, polypropylene of the middle layer at least containing its quality 10-18% enhances composite material;
The polypropylene enhances primary raw material of the composite material using jute as weft-knitted bi-axial fabric, utilizes weft-knitted twin shaft To weaving method biaxially serve as a contrast yarn woven fabric to process jute weft knitting, and it is blended and obtained with the short fibre of polypropylene;
Preferably, the preparation method of the polypropylene enhancing composite material, includes the following steps:Biaxially by jute weft knitting Knitted fabric and the short fibre of polypropylene carry out interval laying, and every layer of megila two sides is covered with the short fibre of a layer polypropylene;Hot press adds The megila of above-mentioned interval laying and the short fibre of polypropylene are placed on hot press to 65 DEG C, are warming up to 92-96 DEG C, add by heat It is depressed into 8-12MPa, pressure maintaining is warming up to 145-148 DEG C, is warming up to 180-190 DEG C after keeping the temperature 5-8min, heat-insulation pressure keeping 10-15min Cooled to room temperature enhances composite material up to polypropylene afterwards;
Biaxially knitted fabric and the short fine laying number of polypropylene are 7-11 layers for the jute weft knitting, refer to jute weft knitting biaxially needle Fabric and the short fine laying number of polypropylene add up to 7-11 layers;
Biaxially knitted fabric and the short fine mass ratio of polypropylene are 1 for the jute weft knitting:1.2-2.
Further, the superficial layer is enhanced by ethylene propylene diene rubber and EPDM cord fabric thread, antistatic agent, glass reinforced plastic Fiber composite is made;It is preferred that vulcanization bonding;
The color of the ethylene propylene diene rubber is red, yellow, green, blue, grey, any one in black;
Glass steel reinforcing fiber of the superficial layer at least containing its quality 8-15%;
Preferably, glass steel reinforcing fiber of the superficial layer at least containing its quality 10-13%;
The glass steel reinforcing fiber is with reinforced plastic glass fibre silk, anti-neutron fiber filament, anti-X, gamma-rays fiber filament, lead Powder, boron carbide powder science compounding, use is blended, impregnate and stoving process is made;
The glass steel reinforcing fiber is mainly prepared by the raw material of following components by weight percent:70-75 parts of reinforced plastic glass fibre silk, prevent 16-20 parts of neutron fiber filament, 12-15 parts of anti-X, gamma-rays fiber filament, 10-15 parts of lead powder, 6-10 parts of boron carbide powder;
Preferably, the preparation method of the glass steel reinforcing fiber, includes the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber filament and anti-X, gamma-rays fiber filament are as the blended system of weft Obtain flat fabric;
2) by unsaturated polyester resin, fire retardant, curing agent and solvent according to mass ratio 100:7-9:1-3:20-25 is uniform Mixing, is made resin solution, and lead powder, boron carbide powder are then added thereto, stirs evenly to obtain lead boron resin solution;
Further, the solvent is the mixing of toluene, dimethylbenzene or both;
Further, the fire retardant is aluminium hydroxide;
Further, the curing agent is polyethylene glycol;
3) flat fabric made from step 1) is impregnated into 50-70min in the lead boron resin solution made from step 2), then Glass steel reinforcing fiber obtained by drying;
Further, dipping is simultaneously in electric field strength 20-40kV/cm, burst length 400-500 μ s, pulse frequency 200- High-pressure pulse electric processing is carried out under the conditions of 300Hz;
Further, the drying is three-stage, i.e. 90-110 DEG C of inducer temperature holding 20-40 minutes, drying section 120-150 DEG C holding 30-50 minutes, holding 20-30 minutes of 70-100 DEG C of outlet section.
Another object of the present invention is to provide the preparation method of above-mentioned hose.
Internal layer, middle layer and the superficial layer of the hose are all made of conventional vulcanization bonding;
As a further improvement of the present invention, for the internal layer of rubber tube, in order to enhance the bonding of inner lining film and rubber layer Property, sided corona treatment is carried out to the adhesive surface of inner lining film and rubber layer respectively, then carries out vulcanization bonding:Curing temperature is preferably 145-165 DEG C, vulcanization time is preferably 35-150min;
Corona principal is that in processed frosting corona discharge, (high-frequency ac voltage is up to using high-frequency high voltage 5000-15000V/m2), low temperature plasma is generated, frosting is made to generate radical reaction and hand over polymer The connection surface is roughening and increases it to the wetability-of polar solvent these gas ions by shocking by electricity and penetrating by the table of print body Its molecular structure is destroyed in face, and then processed surface molecular is aoxidized and polarized, and ion electric shock erosion surface is held so that increasing Print the adhesive ability on object surface.
High-power corona treatment used in the present invention is Nantong Sanxin Plastics Equipment Technology Co., Ltd.'s production, type Number:CW3060, maximum output voltage 15kV, peak power output 60kW, working frequency 15-40KHz;
The inner lining film adhesive surface sided corona treatment technique is:Power 10-15kW, frequency 19-24KHz;Corona intensity is: 43-48mN/m;
The rubber layer adhesive surface sided corona treatment technique is:Power 12-16kW, frequency 22-25KHz;Corona intensity is: 45-49mN/m;
After above-mentioned corona process, the inner lining film and the rubber layer adhesive surface surface tension are significantly improved, table Face tension index averagely improves 7-11mN/m, and very close, along with the inner lining film and the excellent material of the rubber layer Caking property, considerably improves the fastness of subsequent inner lining film and rubber layer vulcanization bonding, and inner lining film is not easy to fall off with rubber layer.
Hose through above method preparation up to arrives the absorptivity of X, gamma-rays and various neutrons in nuclear radiation The bonding force (N/25mm) of 97.5-99.5%, inner lining film and rubber layer reaches 160-180.
In the present invention, the adhesive strength of inner lining film and rubber layer be by disbonded test measure adhesive strength (unit=with 25mm width is the N of unit) obtained value, that is, inner lining film and rubber synusia are bonded, 155 DEG C at a temperature of pressurize sulphur Change 90 minutes, the sheet test film of 25mm wide is made, using autoplotter in room temperature (23 DEG C) with removing in 50mm/ minutes Speed by the sheet test film of acquisition with the angle of 180 degree from liner film stripping, measure above-mentioned adhesive strength.
Beneficial effect:
A kind of hose of the invention, with low density polyethylene (LDPE) (LLDPE), ultra-high molecular weight polyethylene (UHMWPE) and high score Sub- crosslinked polyethylene is primary raw material, science compounding and polyimides, tetrem with good adhesion performance after rubber tube vulcanization The chemical substances such as five amine of base, alpha-sulfo-fatty acid alkyl ester salt, epoxy resin, SBR latex, rosin prepare inner lining film, using same When sided corona treatment is carried out to inner lining film adhesive surface and rubber tube adhesive surface method, to enhance its caking property, and in superficial layer It is compounded with the glass steel reinforcing fiber with shielding property, so that rubber tube superficial layer has excellent anti-radiation performance, especially The pipeline of transfer oil and natural gas is solved because of ionising radiation bring security risk, finally prepares a kind of inner lining film bonding jail Gu anti-radiation performance is strong, can transport the hose of LPG, LNG and strong corrosive chemical solvent, to X in nuclear radiation, gamma-rays and each For the absorptivity of kind of neutron up to 97.5-99.5%, the bonding force (N/25mm) of inner lining film and rubber layer reaches 160-180. Specific test effect is shown in embodiment 6-7
Main technical principle is as follows:
1. inner lining film of the present invention may be the introduction of a large amount of unhindered amina, and with the sulfonated alkyl ester with wettability Salt and with compounding with the epoxy resin of rubber good adhesion, SBR latex and rosin science, glues high molecular polythene film Knot property is improved, and low density polyethylene (LDPE) (LLDPE), ultra-high molecular weight polyethylene (UHMWPE) and high molecular crosslink are being kept Under the characteristic of the excellent material of polyethylene, the defect of its bad adhesion is overcome, so that the inner lining film is with preferable resistance to Under the conditions of the characteristics such as mill property, temperature tolerance, corrosion resistance, oil resistivity, resistance to acid and alkali, self-lubrication, also there is excellent and rubber The performance of bonding.It should be noted that above-mentioned mechanism is the deduction of present inventor etc., though the mechanism of the present application with The mechanism is not inconsistent, and still belongs in the scope of the invention.It should also be noted that, the above-mentioned performance of the inner lining film is its each material Component science compounding, the effect of synergistic effect, the superposition of not simple material function.In fact, the inner lining film with it is existing Technology has excellent adhesive property with after vulcanization of rubber bonding compared to really.
2. glass steel reinforcing fiber of the present invention be with reinforced plastic glass fibre silk, anti-neutron fiber filament, anti-X, gamma-rays fiber filament, Lead powder, boron carbide powder science compounding, use is blended, impregnate and stoving process is made, and not only has light high-strength, anti-aging, resistance to The excellent performances such as burn into is fire-retardant, sunshade, heat-insulated, insulation, and there is shielding fast neutron, thermal neutron and X, gamma-emitting synthesis Shield effectiveness, especially dipping process are managed using high-voltage pulse electric factory and office, so that glass steel reinforcing fiber moderately softens, grid knot Structure is more abundant, accelerates the seepage velocity of lead powder, boron carbide powder, enhances dipping effect, improves pickling efficiency, final to increase The strong radiation-proof effect of glass steel reinforcing fiber.
3. the manufacturing method of polypropylene enhancing composite material of the present invention is compared with prior art, jute is had chosen as weft knitting The primary raw material of bi-axial fabric, the mechanical property and resources advantage that jute can be made full use of excellent;And utilize weft-knitted twin shaft To weaving method biaxially serve as a contrast yarn woven fabric to process jute weft knitting, low in raw material price can save production cost, and exploitation is new The reinforcement of the good environment-friendly composite material of type, while chemical waste is not generated, no pollution to the environment.The polypropylene enhancing Composite material tensile strength is 104.8-112.6MPa, bending strength 120.1-139.8MPa.
4. the preparation method simple process of inventive hose, easy to operate, controllability is good, high-efficient, is produced on a large scale, On the basis of existing vulcanization bonding, sided corona treatment is carried out by the adhesive surface to inner lining film and rubber layer respectively, is significantly improved The surface tension of inner lining film and rubber layer adhesive surface, surface tension exponential average improve 7-11mN/m, and very close, then plus Upper inner lining film and the excellent material caking property of rubber layer considerably improve subsequent inner lining film with rubber layer and vulcanize the secured of bonding Property, inner lining film is not easy to fall off with rubber layer.
Specific embodiment
The present invention is described below by specific embodiment.Unless stated otherwise, technological means used in the present invention It is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, it is not intended to limit the present invention Range, the spirit and scope of the invention are limited only by the claims that follow.To those skilled in the art, without departing substantially from this Under the premise of invention spirit and scope, to the various changes or change of material component and dosage progress in these embodiments It belongs to the scope of protection of the present invention.
Used high-power corona treatment used in following example 1-5 is that plastic cement equipment science and technology is believed in Nantong three Co., Ltd's production, model:CW3060, maximum output voltage 15kV, peak power output 60kW, working frequency 15-40KHz; Other industrial chemicals are commercially available commodity.
Embodiment 1
A kind of hose, including rubber tube body, the rubber tube body successively include internal layer, middle layer and table from inside to outside Surface layer;
The internal layer is bonded by ethylene-propylene-diene monomer glue-line and inner lining film by vulcanization;
The ethylene propylene diene rubber color is milky;
The inner lining film is mainly prepared by the raw material of following parts by weight:30 parts of LLDPE, 25 parts of polyvinyl alcohol, UHMWPE20 parts, 15 parts of high molecular crosslink polyethylene, 9 parts of polyimides, 7 parts of tetraethylenepentamine, alpha-sulfo-fatty acid alkyl ester 6 parts of salt, 6 parts of epoxy resin, 8 parts of SBR latex, 7 parts of rosin;
Blow molding, stretching film forming after the inner lining film is squeezed out raw material using conventional method, inner lining film is with a thickness of 0.42mm.
The middle layer enhances composite material, fire retardant, plating by ethylene propylene diene rubber and EPDM cord fabric thread, polypropylene The vulcanization of brass steel wire bonds;
The middle layer contains the polypropylene enhancing composite material of its quality 15%;
The preparation method of the polypropylene enhancing composite material, includes the following steps:By jute weft knitting biaxially knitted fabric Interval laying is carried out with the short fibre of polypropylene, every layer of megila two sides is covered with the short fibre of a layer polypropylene;Hot press is heated to 65 DEG C, the megila of above-mentioned interval laying and the short fibre of polypropylene are placed on hot press, 94 DEG C is warming up to, is forced into 10MPa, Pressure maintaining is warming up to 147 DEG C, is warming up to 185 DEG C after keeping the temperature 6min, cooled to room temperature is after heat-insulation pressure keeping 12min up to polypropylene Enhance composite material;
Biaxially knitted fabric and the short fine laying number of polypropylene are 9 layers for the jute weft knitting, refer to that jute weft knitting is biaxially knitted Object and the short fine laying number of polypropylene add up to 9 layers;
Biaxially knitted fabric and the short fine mass ratio of polypropylene are 1 for the jute weft knitting:1.25.
The superficial layer is vulcanized by ethylene propylene diene rubber and EPDM cord fabric thread, antistatic agent, glass steel reinforcing fiber Bonding is made;
The color of the ethylene propylene diene rubber is green;
The superficial layer contains the glass steel reinforcing fiber of its quality 11%;
The glass steel reinforcing fiber is mainly prepared by the raw material of following components by weight percent:73 parts of reinforced plastic glass fibre silk, prevent in 18 parts of subbundle silk, 13 parts of anti-X, gamma-rays fiber filament, 12 parts of lead powder, 8 parts of boron carbide powder;
The preparation method of the glass steel reinforcing fiber, includes the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber filament and anti-X, gamma-rays fiber filament are as the blended system of weft Obtain flat fabric;
2) by unsaturated polyester resin, aluminium hydroxide, polyethylene glycol and toluene according to mass ratio 100:8:2:22 is uniformly mixed It closes, resin solution is made, lead powder, boron carbide powder are then added thereto, stirs evenly to obtain lead boron resin solution;
3) flat fabric made from step 1) impregnates to 60min in the lead boron resin solution made from step 2), while High-pressure pulse electric processing is carried out under the conditions of electric field strength 30kV/cm, 450 μ s of burst length, pulse frequency 250Hz;Then it dries Dry glass steel reinforcing fiber to obtain the final product;
It is described drying be three-stage, i.e., 100 DEG C of inducer temperature keep 30 minutes, 135 DEG C of drying section keep 40 minutes, out 85 DEG C of section of mouth are kept for 25 minutes.
Preparation method.
Internal layer, middle layer and the superficial layer of the hose are all made of conventional vulcanization bonding;
Wherein, for the internal layer of rubber tube, in order to enhance the caking property of inner lining film and rubber layer, to inner lining film and rubber layer Adhesive surface carry out sided corona treatment respectively, then carry out vulcanization bonding:155 DEG C of curing temperature, vulcanization time 90min;
The inner lining film adhesive surface sided corona treatment technique is:Power 12kW, frequency 21KHz;Corona intensity is:45mN/m;
The rubber layer adhesive surface sided corona treatment technique is:Power 14kW, frequency 23KHz;Corona intensity is:47mN/m;
Hose through above method preparation up to arrives the absorptivity of X, gamma-rays and various neutrons in nuclear radiation 99.5%, the bonding force (N/25mm) of inner lining film and rubber layer reaches 180.
Embodiment 2
A kind of hose, including rubber tube body, the rubber tube body successively include internal layer, middle layer and table from inside to outside Surface layer;
The internal layer is bonded by ethylene-propylene-diene monomer glue-line and inner lining film by vulcanization;
The ethylene propylene diene rubber color is milky;
The inner lining film is mainly prepared by the raw material of following parts by weight:20 parts of LLDPE, 20 parts of polyvinyl alcohol, UHMWPE 15 parts, 10 parts of high molecular crosslink polyethylene, 8 parts of polyimides, 5 parts of tetraethylenepentamine, 5 parts of alpha-sulfo-fatty acid alkyl ester salt, 5 parts of epoxy resin, 7 parts of SBR latex, 6 parts of rosin;
Blow molding, stretching film forming after the inner lining film is squeezed out raw material using conventional method, inner lining film is with a thickness of 0.35mm.
The middle layer enhances composite material, fire retardant, plating by ethylene propylene diene rubber and EPDM cord fabric thread, polypropylene Brass steel wire vulcanization bonding is made;
The middle layer contains the polypropylene enhancing composite material of its quality 10%;
The preparation method of the polypropylene enhancing composite material, includes the following steps:By jute weft knitting biaxially knitted fabric Interval laying is carried out with the short fibre of polypropylene, every layer of megila two sides is covered with the short fibre of a layer polypropylene;Hot press is heated to 65 DEG C, the megila of above-mentioned interval laying and the short fibre of polypropylene are placed on hot press, 92 DEG C is warming up to, is forced into 8MPa, Pressure maintaining is warming up to 145 DEG C, is warming up to 180 DEG C after keeping the temperature 5min, cooled to room temperature is after heat-insulation pressure keeping 10min up to polypropylene Enhance composite material;
Biaxially knitted fabric and the short fine laying number of polypropylene are 7 layers for the jute weft knitting, refer to that jute weft knitting is biaxially knitted Object and the short fine laying number of polypropylene add up to 7 layers;
Biaxially knitted fabric and the short fine mass ratio of polypropylene are 1 for the jute weft knitting:1.2.
The superficial layer is vulcanized by ethylene propylene diene rubber and EPDM cord fabric thread, antistatic agent, glass steel reinforcing fiber Bonding is made;
The color of the ethylene propylene diene rubber is red;
The superficial layer contains the glass steel reinforcing fiber of its quality 10%;
The glass steel reinforcing fiber is mainly prepared by the raw material of following components by weight percent:70 parts of reinforced plastic glass fibre silk, prevent 16 parts of neutron fiber filament, 12 parts of anti-X, gamma-rays fiber filament, 10 parts of lead powder, 6 parts of boron carbide powder;
The preparation method of the glass steel reinforcing fiber, includes the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber filament and anti-X, gamma-rays fiber filament are as the blended system of weft Obtain flat fabric;
2) by unsaturated polyester resin, aluminium hydroxide, polyethylene glycol and dimethylbenzene according to mass ratio 100:7:1:20 uniformly Mixing, is made resin solution, and lead powder, boron carbide powder are then added thereto, stirs evenly to obtain lead boron resin solution;
3) flat fabric made from step 1) impregnates to 50min in the lead boron resin solution made from step 2), while High-pressure pulse electric processing is carried out under the conditions of electric field strength 20kV/cm, 400 μ s of burst length, pulse frequency 200Hz;Then it dries Dry glass steel reinforcing fiber to obtain the final product;
It is described drying be three-stage, i.e., 90 DEG C of inducer temperature keep 40 minutes, 120 DEG C of drying section keep 50 minutes, out 70 DEG C of section of mouth are kept for 30 minutes.
Preparation method.
Internal layer, middle layer and the superficial layer of the hose are all made of conventional vulcanization bonding;
Wherein, for the internal layer of rubber tube, in order to enhance the caking property of inner lining film and rubber layer, to inner lining film and rubber layer Adhesive surface carry out sided corona treatment respectively, then carry out vulcanization bonding:145 DEG C of curing temperature, vulcanization time 150min;
The inner lining film adhesive surface sided corona treatment technique is:Power 10kW, frequency 19KHz;Corona intensity is:43mN/m;
The rubber layer adhesive surface sided corona treatment technique is:Power 12kW, frequency 22KHz;Corona intensity is:45mN/m;
Hose through above method preparation to the absorptivity of X, gamma-rays and various neutrons in nuclear radiation up to 99%, Inner lining film and the bonding force (N/25mm) of rubber layer reach 175.
Embodiment 3
A kind of hose, including rubber tube body, the rubber tube body successively include internal layer, middle layer and table from inside to outside Surface layer;
The internal layer is bonded by ethylene-propylene-diene monomer glue-line and inner lining film by vulcanization;
The ethylene propylene diene rubber color is milky;
The inner lining film is mainly prepared by the raw material of following parts by weight:40 parts of LLDPE, 30 parts of polyvinyl alcohol, UHMWPE 25 parts, 20 parts of high molecular crosslink polyethylene, 10 parts of polyimides, 8 parts of tetraethylenepentamine, 7 parts of alpha-sulfo-fatty acid alkyl ester salt, 7 parts of epoxy resin, 9 parts of SBR latex, 8 parts of rosin;
Blow molding, stretching film forming after the inner lining film is squeezed out raw material using conventional method, inner lining film is with a thickness of 0.5mm.
The middle layer enhances composite material, fire retardant, plating by ethylene propylene diene rubber and EPDM cord fabric thread, polypropylene Brass steel wire vulcanization bonding is made;
The middle layer contains the polypropylene enhancing composite material of its quality 18%;
The preparation method of the polypropylene enhancing composite material, includes the following steps:By jute weft knitting biaxially knitted fabric Interval laying is carried out with the short fibre of polypropylene, every layer of megila two sides is covered with the short fibre of a layer polypropylene;Hot press is heated to 65 DEG C, the megila of above-mentioned interval laying and the short fibre of polypropylene are placed on hot press, 96 DEG C is warming up to, is forced into 12MPa, Pressure maintaining is warming up to 148 DEG C, is warming up to 190 DEG C after keeping the temperature 8min, cooled to room temperature is after heat-insulation pressure keeping 15min up to polypropylene Enhance composite material;
Biaxially knitted fabric and the short fine laying number of polypropylene are 11 layers for the jute weft knitting, refer to that jute weft knitting is biaxially knitted Object and the short fine laying number of polypropylene add up to 11 layers;
Biaxially knitted fabric and the short fine mass ratio of polypropylene are 1 for the jute weft knitting:2.
The superficial layer is vulcanized by ethylene propylene diene rubber and EPDM cord fabric thread, antistatic agent, glass steel reinforcing fiber Bonding is made;
The color of the ethylene propylene diene rubber is yellow;
The superficial layer contains the glass steel reinforcing fiber of its quality 13%;
The glass steel reinforcing fiber is mainly prepared by the raw material of following components by weight percent:75 parts of reinforced plastic glass fibre silk, prevent 20 parts of neutron fiber filament, 15 parts of anti-X, gamma-rays fiber filament, 15 parts of lead powder, 10 parts of boron carbide powder;
The preparation method of the glass steel reinforcing fiber, includes the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber filament and anti-X, gamma-rays fiber filament are as the blended system of weft Obtain flat fabric;
2) by unsaturated polyester resin, aluminium hydroxide, polyethylene glycol and toluene according to mass ratio 100:9:3:25 is uniformly mixed It closes, resin solution is made, lead powder, boron carbide powder are then added thereto, stirs evenly to obtain lead boron resin solution;
3) flat fabric made from step 1) impregnates to 70min in the lead boron resin solution made from step 2), while High-pressure pulse electric processing is carried out under the conditions of electric field strength 40kV/cm, 500 μ s of burst length, pulse frequency 300Hz;Then it dries Dry glass steel reinforcing fiber to obtain the final product;
It is described drying be three-stage, i.e., 110 DEG C of inducer temperature keep 20 minutes, 150 DEG C of drying section keep 30 minutes, out 100 DEG C of section of mouth are kept for 20 minutes.
Preparation method.
Internal layer, middle layer and the superficial layer of the hose are all made of conventional vulcanization bonding;
Wherein, for the internal layer of rubber tube, in order to enhance the caking property of inner lining film and rubber layer, to inner lining film and rubber layer Adhesive surface carry out sided corona treatment respectively, then carry out vulcanization bonding:Curing temperature is preferably 165 DEG C, and vulcanization time is preferably 35min;
The inner lining film adhesive surface sided corona treatment technique is:Power 15kW, frequency 24KHz;Corona intensity is:48mN/m;
The rubber layer adhesive surface sided corona treatment technique is:Power 16kW, frequency 25KHz;Corona intensity is:49mN/m;
Hose through above method preparation up to arrives the absorptivity of X, gamma-rays and various neutrons in nuclear radiation 98.5%, the bonding force (N/25mm) of inner lining film and rubber layer reaches 170.
Embodiment 4
A kind of hose, including rubber tube body, the rubber tube body successively include internal layer, middle layer and table from inside to outside Surface layer;
The internal layer is bonded by ethylene-propylene-diene monomer glue-line and inner lining film by vulcanization;
The ethylene propylene diene rubber color is milky;
The inner lining film is mainly prepared by the raw material of following parts by weight:20 parts of LLDPE, 30 parts of polyvinyl alcohol, UHMWPE 15 parts, 20 parts of high molecular crosslink polyethylene, 8 parts of polyimides, 8 parts of tetraethylenepentamine, 5 parts of alpha-sulfo-fatty acid alkyl ester salt, 7 parts of epoxy resin, 7 parts of SBR latex, 8 parts of rosin;
Blow molding, stretching film forming after the inner lining film is squeezed out raw material using conventional method, inner lining film is with a thickness of 0.4mm.
The middle layer enhances composite material, fire retardant, plating by ethylene propylene diene rubber and EPDM cord fabric thread, polypropylene Brass steel wire vulcanization bonding is made;The middle layer contains the polypropylene enhancing composite material of its quality 5%;
The preparation method of the polypropylene enhancing composite material, includes the following steps:By jute weft knitting biaxially knitted fabric Interval laying is carried out with the short fibre of polypropylene, every layer of megila two sides is covered with the short fibre of a layer polypropylene;Hot press is heated to 65 DEG C, the megila of above-mentioned interval laying and the short fibre of polypropylene are placed on hot press, 92 DEG C is warming up to, is forced into 12MPa, Pressure maintaining is warming up to 145 DEG C, is warming up to 180 DEG C after keeping the temperature 8min, cooled to room temperature is after heat-insulation pressure keeping 15min up to polypropylene Enhance composite material;
Biaxially knitted fabric and the short fine laying number of polypropylene are 9 layers for the jute weft knitting, refer to that jute weft knitting is biaxially knitted Object and the short fine laying number of polypropylene add up to 9 layers;
Biaxially knitted fabric and the short fine mass ratio of polypropylene are 1 for the jute weft knitting:1.25.
The superficial layer is vulcanized by ethylene propylene diene rubber and EPDM cord fabric thread, antistatic agent, glass steel reinforcing fiber Bonding is made;
The color of the ethylene propylene diene rubber is blue;
The superficial layer contains the glass steel reinforcing fiber of its quality 8%;
The glass steel reinforcing fiber is mainly prepared by the raw material of following components by weight percent:70 parts of reinforced plastic glass fibre silk, prevent 20 parts of neutron fiber filament, 12 parts of anti-X, gamma-rays fiber filament, 15 parts of lead powder, 6 parts of boron carbide powder;
The preparation method of the glass steel reinforcing fiber, includes the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber filament and anti-X, gamma-rays fiber filament are as the blended system of weft Obtain flat fabric;
2) by unsaturated polyester resin, aluminium hydroxide, polyethylene glycol and solvent according to mass ratio 100:7:3:20 is uniformly mixed It closes, resin solution is made, lead powder, boron carbide powder are then added thereto, stirs evenly to obtain lead boron resin solution;
Further, the solvent is toluene, dimethylbenzene in mass ratio 1:1 uniformly mixing;
3) flat fabric made from step 1) is impregnated into 60min in the lead boron resin solution made from step 2), then dried Dry glass steel reinforcing fiber to obtain the final product;
Preparation method.
Internal layer, middle layer and the superficial layer of the hose are all made of conventional vulcanization bonding;
Wherein, for the internal layer of rubber tube, in order to enhance the caking property of inner lining film and rubber layer, to inner lining film and rubber layer Adhesive surface carry out sided corona treatment respectively, then carry out vulcanization bonding:145 DEG C of curing temperature, vulcanization time 35min;
The inner lining film adhesive surface sided corona treatment technique is:Power 10kW, frequency 24KHz;Corona intensity is:46mN/m;
The rubber layer adhesive surface sided corona treatment technique is:Power 12kW, frequency 25KHz;Corona intensity is:47mN/m;
Hose through above method preparation up to arrives the absorptivity of X, gamma-rays and various neutrons in nuclear radiation 97.5%, the bonding force (N/25mm) of inner lining film and rubber layer reaches 160.
Embodiment 5
A kind of hose, including rubber tube body, the rubber tube body successively include internal layer, middle layer and table from inside to outside Surface layer;
The internal layer is bonded by ethylene-propylene-diene monomer glue-line and inner lining film by vulcanization;
The ethylene propylene diene rubber color is milky;
The inner lining film is mainly prepared by the raw material of following parts by weight:40 parts of LLDPE, 20 parts of polyvinyl alcohol, UHMWPE 25 parts, 10 parts of high molecular crosslink polyethylene, 10 parts of polyimides, 5 parts of tetraethylenepentamine, 7 parts of alpha-sulfo-fatty acid alkyl ester salt, 5 parts of epoxy resin, 9 parts of SBR latex, 6 parts of rosin;
Blow molding, stretching film forming after the inner lining film is squeezed out raw material using conventional method, inner lining film is with a thickness of 0.4mm.
The middle layer enhances composite material, fire retardant, plating by ethylene propylene diene rubber and EPDM cord fabric thread, polypropylene Brass steel wire vulcanization bonding is made;The middle layer contains the polypropylene enhancing composite material of its quality 30%;
The preparation method of the polypropylene enhancing composite material, includes the following steps:By jute weft knitting biaxially knitted fabric Interval laying is carried out with the short fibre of polypropylene, every layer of megila two sides is covered with the short fibre of a layer polypropylene;Hot press is heated to 65 DEG C, the megila of above-mentioned interval laying and the short fibre of polypropylene are placed on hot press, 92 DEG C is warming up to, is forced into 12MPa, Pressure maintaining is warming up to 145 DEG C, is warming up to 180 DEG C after keeping the temperature 8min, cooled to room temperature is after heat-insulation pressure keeping 15min up to polypropylene Enhance composite material;
Biaxially knitted fabric and the short fine laying number of polypropylene are 9 layers for the jute weft knitting, refer to that jute weft knitting is biaxially knitted Object and the short fine laying number of polypropylene add up to 9 layers;
Biaxially knitted fabric and the short fine mass ratio of polypropylene are 1 for the jute weft knitting:1.25.
The superficial layer is vulcanized by ethylene propylene diene rubber and EPDM cord fabric thread, antistatic agent, glass steel reinforcing fiber Bonding is made;
The color of the ethylene propylene diene rubber is black;
The superficial layer contains the glass steel reinforcing fiber of its quality 15%;
The glass steel reinforcing fiber is mainly prepared by the raw material of following components by weight percent:75 parts of reinforced plastic glass fibre silk, prevent 16 parts of neutron fiber filament, 15 parts of anti-X, gamma-rays fiber filament, 10 parts of lead powder, 10 parts of boron carbide powder;
The preparation method of the glass steel reinforcing fiber, includes the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber filament and anti-X, gamma-rays fiber filament are as the blended system of weft Obtain flat fabric;
2) by unsaturated polyester resin, fire retardant, curing agent and solvent according to mass ratio 100:8:2:23 uniformly mixing, system At resin solution, lead powder, boron carbide powder are then added thereto, stirs evenly to obtain lead boron resin solution;
3) flat fabric made from step 1) is impregnated into 60min in the lead boron resin solution made from step 2), then dried Dry glass steel reinforcing fiber to obtain the final product;
Preparation method.
Internal layer, middle layer and the superficial layer of the hose are all made of conventional vulcanization bonding;
Wherein, for the internal layer of rubber tube, in order to enhance the caking property of inner lining film and rubber layer, to inner lining film and rubber layer Adhesive surface carry out sided corona treatment respectively, then carry out vulcanization bonding:Curing temperature is 165 DEG C, vulcanization time 150min;
The inner lining film adhesive surface sided corona treatment technique is:Power 13kW, frequency 21KHz;Corona intensity is:46mN/m;
The rubber layer adhesive surface sided corona treatment technique is:Power 15kW, frequency 24KHz;Corona intensity is:48mN/m;
Hose through above method preparation to the absorptivity of X, gamma-rays and various neutrons in nuclear radiation up to 98%, Inner lining film and the bonding force (N/25mm) of rubber layer reach 172.
6 inventive hose inner lining film of embodiment and rubber layer adhesion strength comparative test
1. experimental program:Using 1-5 of the embodiment of the present invention as test group, the conditions such as other materials, Processes and apparatus are identical In the case of, only inner lining film is different, in contrast organizes 1 for the best corrosion-proof lining film of caking property;Other materials, Processes and apparatus Etc. in the identical situation of conditions, only do not use sided corona treatment inner lining film and rubber layer adhesive surface in contrast to organize 2;Other materials In the identical situation of the conditions such as material, Processes and apparatus, only bonding mode is changed to directly bond in contrast group using adhesive 3;Then above-mentioned several scheme lower liner films and rubber layer adhesion strength are measured, such as table 1:
2. measuring method:The adhesive strength of inner lining film and rubber layer be by disbonded test measure adhesive strength (unit= N as unit of 25mm width) obtained value, that is, inner lining film and rubber synusia are bonded, 155 DEG C at a temperature of pressurize Vulcanization 90 minutes makes the sheet test film of 25mm wide, using autoplotter in room temperature (23 DEG C) with stripping in 50mm/ minutes From speed by the sheet test film of acquisition with the angle of 180 degree from liner film stripping, measure above-mentioned adhesive strength.
1. inner lining film of table and rubber layer adhesion strength contrast test result (unit:N/25mm)
Project Test group Control group 1 Control group 2 Control group 3
Embodiment 1 180 135 160 175
Embodiment 2 175 128 156 172
Embodiment 3 170 122 153 165
Embodiment 4 160 118 145 152
Embodiment 5 172 130 155 160
The above results are counted, the contribution rate to contribute to inner lining film excellent adhesion of the present invention is:Liner is thin 20-28%;Sided corona treatment 9-11%;Bonding mode 2-5%;Show:Compared with prior art, at inner lining film and corona of the present invention The method for managing bonding surface is to generate the basic reason of significant bond effect, although bonding mode has a fixing to adhesion strength It rings, but less, can preferably vulcanize the bonding mode of bonding.
The test of 7 inventive hose shielding property of embodiment
(contained with the hose and the commercially available anti-corrosive rubber pipe with certain shielding property of 1-5 of embodiment of the present invention preparation Have reinforced plastic glass fibre layer) it is subjects, carry out the test of core spoke transmitance, specific test data such as table 2
Table 2
Fast neutron transmitance Slow neutron transmitance X, gamma-rays transmitance Thermal neutron transmitance
It is commercially available 14% 18% 93% 95%
Embodiment 1 0.1% 0.1% 0.2% 0.1%
Embodiment 2 0.2% 0.2% 0.3% 0.3%
Embodiment 3 0.3% 0.3% 0.5% 0.4%
Embodiment 4 0.5% 0.6% 0.7% 0.7%
Embodiment 5 0.2% 0.3% 0.7% 0.8%
As seen from the above table, the commercially available rubber tube containing reinforced plastic glass fibre layer although can be absorbed most of fast neutron and it is slow in Son, but to X, gamma-rays and thermal neutron almost without absorption function, rubber tube radiation-proof effect is poor, hose prepared by the present invention With stronger anti-radiation performance, the absorptivity of X, gamma-rays and various neutrons in nuclear radiation may be up to 97.5-99.5%, it is non- It is often suitable as the pipeline of transfer oil and natural gas, is avoided because of ionising radiation bring security risk.
The test of 8 inventive hose quantitative measurement of embodiment
Hose prepared by the embodiment of the present invention 1 takes test model by standard, is respectively put into the sulphur that mass fraction is 30% In the sour sodium hydroxide solution with 30%, strong acid, highly basic, high temperature corrosion-resisting test are carried out, has corroded 72h with this condition, so Style is taken out afterwards and measures physical properties index, as a result such as table 3:
3 hose segment quantitative measurement result of table
Physical property Embodiment 1 30% caustic soda corrodes 72h 30% sulfuric acid corrosion 72h
Tensile strength MPa 32.25 32.18 32.11
Elongation rate of tensile failure % 650.56 586.77 576.84
Tearing strength N/mm 106.28 98.56 95.67
Relative volume abrasion loss mm3 68.33 70.65 71.48
Hardness A 86 85 84
Resilience % 12 16 14
The above result shows that:Inventive hose has excellent resistance to acid and alkali, corrosion resistance, wearability, resilience, heatproof Property and tear resistance, have excellent physical property.

Claims (6)

1. a kind of hose, including rubber tube body, which is characterized in that the rubber tube body from inside to outside successively include internal layer, Middle layer and superficial layer;The internal layer is oil resistant, anti-corrosion layer;The middle layer is fire-retardant, enhancement layer;The superficial layer is anti- Electrostatic, radiation protective layer;
The internal layer is bonded by ethylene-propylene-diene monomer glue-line and inner lining film by vulcanization;The internal layer inner lining film and rubber layer Adhesive surface carries out sided corona treatment respectively;
The inner lining film is mainly prepared by the raw material of following parts by weight:20-40 parts of linear low density polyethylene (LLDPE), polyvinyl alcohol 20-30 parts, 15-25 parts of ultra-high molecular weight polyethylene, 10-20 parts of high molecular crosslink polyethylene, 8-10 parts of polyimides, tetraethyl Five 5-8 parts of amine, 5-7 parts of alpha-sulfo-fatty acid alkyl ester salt, 5-7 parts of epoxy resin, 7-9 parts of SBR latex, 6-8 parts of rosin;
The superficial layer is bonded by ethylene propylene diene rubber and EPDM cord fabric thread, antistatic agent, glass steel reinforcing fiber vulcanization It is made;The superficial layer contains the glass steel reinforcing fiber 8-15% of its quality;
The glass steel reinforcing fiber is mainly prepared by the raw material of following components by weight percent:70-75 parts of reinforced plastic glass fibre silk, anti-neutron 16-20 parts of fiber filament, 12-15 parts of anti-X, gamma-rays fiber filament, 10-15 parts of lead powder, 6-10 parts of boron carbide powder;
The preparation method of the glass steel reinforcing fiber, includes the following steps:
1) it is put down reinforced plastic glass fibre silk as warp, anti-neutron fiber filament and anti-X, gamma-rays fiber filament as blended be made of weft Face fabric;
2) by unsaturated polyester resin, fire retardant, curing agent and solvent according to mass ratio 100:7-9:1-3:20-25 is uniformly mixed It closes, resin solution is made, lead powder, boron carbide powder are then added thereto, stirs evenly to obtain lead boron resin solution;
3) flat fabric made from step 1) is impregnated into 50-70min in the lead boron resin solution made from step 2), then dried Up to glass steel reinforcing fiber;
In electric field strength 20-40kV/cm, burst length 400-500 μ s, pulse frequency 200-300Hz while step 3) impregnates Under the conditions of carry out high-pressure pulse electric processing;
The middle layer enhances composite material, fire retardant, brass plating by ethylene propylene diene rubber and EPDM cord fabric thread, polypropylene Steel wire vulcanization bonding is made;The middle layer contains the polypropylene enhancing composite material 5-30% of its quality;
The preparation method of the polypropylene enhancing composite material, includes the following steps:By jute weft knitting biaxially knitted fabric and poly- The short fibre of propylene carries out interval laying, and every layer of megila two sides is covered with the short fibre of a layer polypropylene;Hot press is heated to 65 DEG C, will The megila and the short fibre of polypropylene of above-mentioned interval laying are placed on hot press, are warming up to 92-96 DEG C, are forced into 8-12MPa, Pressure maintaining is warming up to 145-148 DEG C, is warming up to 180-190 DEG C after keeping the temperature 5-8min, naturally cools to after heat-insulation pressure keeping 10-15min Room temperature enhances composite material up to polypropylene.
2. hose as described in claim 1, which is characterized in that the inner lining film adhesive surface sided corona treatment technique is:Power 10- 15kW, frequency 19-24KHz;The rubber layer adhesive surface sided corona treatment technique is:Power 12-16kW, frequency 22-25KHz.
3. hose as claimed in claim 1 or 2, which is characterized in that the glass reinforced plastic enhancing that the superficial layer contains its quality is fine Tie up 10-13%.
4. hose as claimed in claim 1 or 2, which is characterized in that the polypropylene enhancing that the middle layer contains its quality is multiple Condensation material 10-18%.
5. hose as claimed in claim 1 or 2, which is characterized in that in the preparation method of the polypropylene enhancing composite material, Biaxially knitted fabric and the short fine laying number of polypropylene are 7-11 layers for the jute weft knitting.
6. hose as claimed in claim 1 or 2, which is characterized in that in the preparation method of the polypropylene enhancing composite material, Biaxially knitted fabric and the short fine mass ratio of polypropylene are 1 for the jute weft knitting:1.2-2.
CN201810802931.1A 2015-09-16 2015-09-16 A kind of hose Pending CN108895216A (en)

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CN201810803489.4A Pending CN108825892A (en) 2015-09-16 2015-09-16 A kind of hose
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CN201710975949.7A Pending CN107588251A (en) 2015-09-16 2015-09-16 A kind of preparation method of flexible pipe
CN201810803487.5A Pending CN108895217A (en) 2015-09-16 2015-09-16 A kind of hose

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CN105065804A (en) 2015-11-18
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CN105065804B (en) 2018-09-11
CN108825892A (en) 2018-11-16

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Application publication date: 20181127