CN105061882A - Flame retarding rubber hose and preparation method thereof - Google Patents
Flame retarding rubber hose and preparation method thereof Download PDFInfo
- Publication number
- CN105061882A CN105061882A CN201510591291.0A CN201510591291A CN105061882A CN 105061882 A CN105061882 A CN 105061882A CN 201510591291 A CN201510591291 A CN 201510591291A CN 105061882 A CN105061882 A CN 105061882A
- Authority
- CN
- China
- Prior art keywords
- layer
- rubber
- lining film
- inner lining
- rubber hose
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/285—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
- B32B2323/046—LDPE, i.e. low density polyethylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/16—EPDM, i.e. ethylene propylene diene monomer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/068—Ultra high molecular weight polyethylene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a flame retarding rubber hose and a preparation method thereof. Low-density polyethylene, ultrahigh molecular weight polyethylene and macromolecule crosslinked polyethylene are taken as raw materials, after scientific compound and vulcanization of the rubber hose, a chemical substance with excellent adhesive property is used for preparing a lining film, the adhering surface of the lining film and the adhering surface of the rubber hose are subject to corona treatment, and glass steel reinforced fibers with radiation resistance are compounded at a surface layer, so the surface layer of the rubber hose has excellent radiation resistance, safety loopholes of a conveying pipeline caused by ionizing radiation are solved, the lame retarding rubber hose with firm adhering of the lining film, high radiation resistance and capability of conveying LPG, LNG and high corrosion chemical solvents is finally prepared, absorptivity for X ray, gamma ray and various neutrons in nuclear radiation is as high as 97.5 to 99.5%, and the adhesive force (N/25mm) of the lining film and the rubber layer is up to 160 to 180.
Description
Technical field
The present invention relates to the preparation of rubber hose, particularly a kind of flame retardant rubber pipe and preparation method thereof.
Background technology
The rubber pipe racks industry of China was through the development of more than 50 years, indispensable supporting effect is served to national economy, especially along with raising and the new diseases of China's Mechanization Level, rubber pipe racks industry constantly and association area interpenetrate, opened up range of application and the field of rubber pipe racks, product is widely used in the fields such as coal, metallurgy, cement, harbour, mine, oil, automobile, weaving, light industry, engineering machinery, building, ocean, agricultural, Aeronautics and Astronautics.In recent years, rubber pipe racks industry adheres to the Scientific Outlook on Development, the kind of product, specification, quality obtain lasting, quick, coordinate, healthy development, substantially meet the demand of domestic market, improve the competitiveness in the international market of product.
At present, China has become rubber pipe racks Production and consumption big country of the world.The rubber pipe racks manufacturing enterprise 812 that the whole nation is of certain scale.According to glue tube belt branch of rubber industry association statistics, the annual production of current national conveying belt reaches 3.6 hundred million m
2, V is with output to reach 2,100,000,000 Am, and sebific duct output reaches 6.6 hundred million Bm, and product production all ranks world's anteposition.2010, China's rubber pipe racks manufacturing income scale reached 223.62 hundred million yuan.Meanwhile, since Eleventh Five-Year Plan, the research and development of China's rubber pipe racks industry specialty are in continuous progress, not only existing rubber pipe racks is improved in sizing material, technique, performance and cost, make it constantly to meet user require and adapt to market demand, and continually develop product innovation and new technology, fill the domestic gaps, the performance of many domestic glue tube belts is close or reach advanced world standards, and this creates condition for home products squeezes into the international market further.Look into according to prediction network regulation, " 12 " period, Chinese national economy also will keep sustainable development, drive the industrial expansions such as coal, iron and steel, cement, harbour, mine, oil, automobile, weaving, light industry, machinery, this brings good opportunity by giving the development of rubber pipe racks industry, estimates that rubber pipe racks manufacturing marketing scale in 2015 will reach 36,000,000,000 yuan.
Production method has shaping and steam vulcanization method, and product performance is rubber hose series product, have oil resistant, acid and alkali-resistance, the characteristic such as heat-resisting, withstand voltage conveying and attract rubber hose.Most of rubber hose has nontoxic, environmental protection, but the Oil/Gas Pipe that ask for something is higher, in elastomeric material, with the addition of fire retardant, in fire retardant, can minimal effect be produced containing hazardous and noxious substances to human body and air.The characteristic of rubber hose also has; Physiological inertia, UV resistant, resistance to ozone, high-low temperature resistant (-80 to 300 degree), transparency is high, screen resilience is strong, and compression is the performance such as indeformable, oil resistant, resistance to punching press, acid and alkali-resistance, wear-resisting, difficult combustion, proof voltage, conduction forever.Its material has numerous species according to the difference of complete processing, and such as NBR paracril is widely used in brake vacuum pipe, and the good gel content of oil-proofness is high, but resistance to ozone is relatively poor; EPDM terpolymer EP rubber is used for automobile water pipe series, as radiator rubber hose, air-conditioner pipe etc.Also has the material that some performances are higher, as AEM acrylic ester high-temperature etc.Often kind of rubber has its characteristic, therefore particularly important on sebific duct select materials.Substantially the material of high-grade car use is relatively better, one slightly car, minibus use material poor, as one slightly car at present also have use paracril as fuelpipe, current paracril is all not suitable for prime the fuel system, and substitute chlorohydrin rubber fluorine sebific duct Application comparison extensive.
Disclosed rubber hose product and preparation method thereof is more: application number be 201220320377.1 Chinese patent disclose a kind of novel hydraulic oil transportation rubber hose, be specially and a kind of there is anti-electrostatic, high-low temperature resistant and rubber transition pipeline that is ageing-resistant, corrosion-resistant, flame-proof environmental protection.Transition pipeline structure comprises upper layer, middle layer and internal layer three layers.Upper layer is by having the good terpolymer EP rubber of anti-electrostatic, high-low temperature resistant, ageing-resistant performance and fabrics of polyester is composited, middle layer is have the ethylene propylene rubber of anti-flaming function and braided steel wire compound is made, and internal layer is made up of the paracril with good oil resistance.Transition pipeline has good oil-proofness, resistant of high or low temperature, ageing-resistant performance, can increase the service life and rubber hose structure is simple, mechanical property good, with low cost.Application number be 201510049105.0 Chinese patent disclose a kind of heat-and corrosion-resistant rubber hose, relate to sebific duct manufacturing technology field, include rubber hose body, described rubber hose body comprises the inner rubber layer, cord body, middle rubber layer, Coppered Steel Wire braid and the outer rubber layer that set gradually from inside to outside, described inner rubber layer is fluororubber layer, and described middle rubber layer and described outer rubber layer are styrene-butadiene rubber(SBR) layer; Described inner rubber layer, described cord body, described middle rubber layer, described Coppered Steel Wire braid are connected with described outer rubber layer sulfuration, compared with prior art, thermotolerance and the erosion resistance of heat-and corrosion-resistant rubber hose of the present invention increase substantially, and satisfied conveying has the needs of certain corrosive high-temperature gas or liquid.Application number be 201310635893.2 Chinese patent disclose a kind of anti-corrosive rubber tube material, it is characterized in that, feed components is composed as follows according to weight part: ethylene-propylene rubber(EPR) 30-40 part, solution polymerized butadiene styrene rubber 25-30 part, SRR-16 reclaimed rubber 15-20 part, benzoyl peroxide 1-2 part, NXT silane coupling agent 3-4 part, nano-graphite 4-7 part, paraffin 7-9 part, talcum 3-4 powder, zinc oxide 0.7-0.9 part, Zinic stearas 0.6-0.8 part, epoxy resin 2-4 part, hexa-methylene-1, the two thiosulfuric acid disodium 0.7-0.9 part of 6-, titanium dioxide 1.5-1.8 part, white oil 1-3 part, oxidation inhibitor AT-100.3-0.5 part, Yoshinox BHT 0.8 part, sulphur 2-4 part.Obtained hose material all has good resistance to various polar chemical product such as acid, alkali, oxygenant etc., and not easily aging, low raw-material cost, excellent product performance, have a extensive future.Application number be 200810224959.8 Chinese patent disclose a kind of preparation method of carbon nanotube-natural rubber compound material, it is characterized in that using epoxy natural rubber as the compatilizer between carbon nanotube and natural rubber, utilize consistency excellent between epoxy natural rubber and natural rubber, and the chemical reaction between epoxy natural rubber and carbon nanotube, improve the dispersion effect of carbon nanotube in natural rubber, strengthen the interaction between carbon nanotube and natural rubber, prepare high-performance carbon nanotube-native rubber composite material; The tensile strength of the sulfide film of this matrix material is 26 ~ 30MPa, and elongation rate of tensile failure is 750 ~ 900%, 300% stress at definite elongation is 4.0 ~ 6.0MPa.Above-mentioned disclosed patent is mainly improved from performances such as corrosion-resistant, ageing-resistant, resistance to temperature, acid and alkali-resistance, flame retardant resistance, physical strengths, consider that preservative coat comes off the also less of problem, yet there are no the relevant report of relevant radiation-proof rubber pipe, this is that the pipeline of transfer oil and Sweet natural gas brings major safety risks.
But for corrosion resistant rubber hose, inner wall section macromolecular lining film is that rot-resistant is crucial, and domestic technique is difficult to reach inner lining film and sebific duct body compact siro spinning technology, easily comes off.Application number be 201180075440.8 Chinese patent disclose the outstanding rubber/plastics composite soft tube of the binding property of a kind of resin layer and rubber layer, as solution, this invention provides a kind of rubber/plastics composite soft tube, there is interior pipe, the standby resin layer as innermost layer of described interior pipe also possesses the rubber layer adjacent with described innermost layer, the material that described resin layer uses is the resin combination containing resin, described resin is at least containing the ionomer possessing carboxylic metallic salt, the material that described rubber layer uses is the rubber combination containing rubber, described rubber is at least containing epoxidezed rubber.This application contriver etc. thinks, why resin layer and rubber layer can bond may be that the epoxy group(ing) had due to carboxylic metallic salt and epoxidezed rubber there occurs reaction.Rubber hose disclosed in this patent does not have radiation-resistant functional equally, and the cohesiveness of resin layer and rubber layer is still not bery desirable.
Therefore, how to make macromolecular lining film preservative coat cohesiveness excellent, and the flame retardant rubber pipe of carried LPG, the LNG and severe corrosive chemical solvents with good radiativity is the unremitting pursue of those skilled in the art.
Summary of the invention
Technical problem solved by the invention is the defect overcoming existing anti-corrosive rubber pipe, with Low Density Polyethylene (LLDPE), ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) and high molecular crosslink polyethylene are main raw material, science composite with rubber hose sulfuration after there is the polyimide of good adhesion performance, tetraethylenepentamine, alpha-sulfo-fatty acid alkyl ester salt, epoxy resin, SBR latex, the chemical substances such as rosin prepare inner lining film, adopt the method for simultaneously inner lining film adhesive surface and rubber hose adhesive surface being carried out to corona treatment, to strengthen its cohesiveness, and the glass steel reinforcing fiber with shielding property is compounded with at upper layer, rubber hose upper layer is made to have excellent anti-radiation, especially the potential safety hazard that the pipeline solving transfer oil and Sweet natural gas brings because of ionizing rays, a kind of inner lining film bonding of final preparation firmly, anti-radiation is strong, LPG can be carried, the flame retardant rubber pipe of LNG and severe corrosive chemical solvents.
In order to achieve the above object, the present invention is by the following technical solutions:
A kind of flame retardant rubber pipe, comprise rubber hose body, described rubber hose body comprises internal layer, middle layer and upper layer from inside to outside successively;
Described internal layer is oil resistant, anti-corrosion layer;
Described middle layer is fire-retardant, enhancement Layer;
Described upper layer is antistatic, radiation protective layer;
Further, described internal layer is at least formed by sulfuration bonding by ethylene-propylene-diene monomer glue-line and the inner lining film with good adhesion performance;
Described terpolymer EP rubber color is oyster white;
The material of preparing of described inner lining film mainly to comprise in linear low density of polyethylene (LLDPE), ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) and high molecular crosslink polyethylene one or more, and inner lining film thickness is 0.35-0.5mm;
Preferably, described inner lining film is prepared primarily of the raw material of following parts by weight: LLDPE20-40 part, polyvinyl alcohol 20-30 part, UHMWPE15-25 part, high molecular crosslink polyethylene 22-32 part, polyimide 8-10 part, tetraethylenepentamine 5-8 part, alpha-sulfo-fatty acid alkyl ester salt 5-7 part, epoxy resin 8-10 part, SBR latex 4-6 part, rosin 3-5 part;
Described inner lining film adopts ordinary method raw material to be extruded rear blowing, stretching film forming.
Further, described middle layer is woven compound made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, polypropylene reinforced composite, fire retardant, brass-plated steel wire; Preferred sulfuration bonding;
The polypropylene reinforced composite of described middle layer at least containing its quality 5-30%;
Preferably, the polypropylene reinforced composite of described middle layer at least containing its quality 10-18%;
The main raw material of described polypropylene reinforced composite using jute as weft-knitted bi-axial fabric, utilizes weft-knitted biax weaving method biaxially to serve as a contrast yarn woven fabric to process jute weft knitting, and obtains with the blending of polypropylene short fiber;
Preferably, the preparation method of described polypropylene reinforced composite, comprise the steps: by jute weft knitting biaxially knitted fabrics and polypropylene short fiber carry out interval laying, every layer of megila two sides is all covered with a layer polypropylene short fiber; Thermocompressor is heated to 65 DEG C, the megila of above-mentioned interval laying and polypropylene short fiber are placed on thermocompressor, be warmed up to 92-96 DEG C, be forced into 8-12MPa, pressurize is warming up to 145-148 DEG C, be warming up to 180-190 DEG C after insulation 5-8min, naturally cool to room temperature after heat-insulation pressure keeping 10-15min and namely obtain polypropylene reinforced composite;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber laying number is 7-11 layer, refers to that biaxially knitted fabrics and polypropylene short fiber laying number add up to 7-11 layer in jute weft knitting;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber mass ratio is 1:1.2-2.
Further, described upper layer is made up of terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, static inhibitor, glass steel reinforcing fiber compound; Preferred sulfuration bonding;
The color of described terpolymer EP rubber is any one in redness, yellow, green, blueness, grey, black;
The glass steel reinforcing fiber of described upper layer at least containing its quality 8-15%;
Preferably, the glass steel reinforcing fiber of described upper layer at least containing its quality 10-13%;
Described glass steel reinforcing fiber is composite with reinforced plastic glass fibre silk, anti-neutron fiber yarn, anti-X, gamma-rays fiber yarn, lead powder, boron carbide powder science, adopts blending, dipping and stoving process to make;
Described glass steel reinforcing fiber is prepared primarily of the raw material of following components by weight percent: reinforced plastic glass fibre silk 70-75 part, anti-neutron fiber yarn 16-20 part, anti-X, gamma-rays fiber yarn 12-15 part, lead powder 10-15 part, boron carbide powder 6-10 part;
Preferably, the preparation method of described glass steel reinforcing fiber, comprises the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber yarn and anti-X, gamma-rays fiber yarn obtain flat fabric as parallel blending;
2) by unsaturated polyester resin, fire retardant, solidifying agent and solvent according to mass ratio 100:7-9:1-3:20-25 Homogeneous phase mixing, make resin solution, then add lead powder, boron carbide powder wherein, stir to obtain plumbous boron resin solution;
Further, described solvent is toluene, dimethylbenzene or the mixing of the two;
Further, described fire retardant is aluminium hydroxide;
Further, described solidifying agent is polyoxyethylene glycol;
3) by step 1) obtained flat fabric is in step 2) flood 50-70min in obtained plumbous boron resin solution, then dry and obtain glass steel reinforcing fiber;
Further, dipping is simultaneously at strength of electric field 20-40kV/cm, and burst length 400-500 μ s, carries out pulsed electric field process under pulse-repetition 200-300Hz condition;
Further, described oven dry is syllogic, and namely inlet section temperature 90-110 DEG C keeps 20-40 minute, drying section 120-150 DEG C to keep 30-50 minute, outlet section 70-100 DEG C to keep 20-30 minute.
Another object of the present invention is to provide the preparation method of above-mentioned rubber hose.
The internal layer of described rubber hose, middle layer and upper layer all adopt conventional sulfuration bonding;
As a further improvement on the present invention, for the internal layer of rubber hose, in order to strengthen the cohesiveness of inner lining film and rubber layer, respectively corona treatment is carried out to the adhesive surface of inner lining film and rubber layer, then carry out sulfuration bonding: curing temperature is preferably 145-165 DEG C, curing time is preferably 35-150min;
Corona principal utilizes high frequency high-voltage at processed frosting corona discharge (high-frequency ac voltage is up to 5000-15000V/m2), and produce low-temperature plasma, make frosting produce free radical reaction and make polymkeric substance occur to be cross-linked. surperficial roughen also increases its wettability to polar solvent-these gas ions by shocking by electricity and penetrating into by its molecular structure of surface breakdown of print body, and then by the oxidation of processed surface molecular and polarization, ion electric shock erosion surface, so that increase the adhesive ability on stock surface
.
High-power corona treatment used in the present invention is that Nantong Sanxin Plastics Equipment Technology Co., Ltd. produces, model: CW3060, maximum output voltage 15kV, peak power output 60kW, operating frequency 15-40KHz;
Described inner lining film adhesive surface corona treatment technique is: power 10-15kW, frequency 19-24KHz; Corona intensity is: 43-48mN/m;
Described rubber layer adhesive surface corona treatment technique is: power 12-16kW, frequency 22-25KHz; Corona intensity is: 45-49mN/m;
After above-mentioned corona art breading, described inner lining film and described rubber layer adhesive surface surface tension significantly improve, surface tension exponential average improves 7-11mN/m, and closely, add described inner lining film and the excellent material binding of described rubber layer, considerably improve the stability that follow-up inner lining film and rubber layer sulfuration bond, inner lining film not easily comes off with rubber layer.
The rubber hose prepared through aforesaid method can up to arriving 97.5-99.5% to the specific absorption of X, gamma-rays and various neutron in nuclear radiation, and the bounding force (N/25mm) of inner lining film and rubber layer reaches 160-180.
In the present invention, the bond strength of inner lining film and rubber layer measures by stripping test the value that bond strength (unit=N) in units of 25mm width obtains, namely, by inner lining film and the laminating of rubber synusia, press vulcanization 90 minutes at the temperature of 155 DEG C, make the sheet test film that 25mm is wide, use autoplotter to peel off from inner lining film with the angle of 180 degree with the sheet test film of the peeling rate of 50mm/ minute by acquisition in room temperature (23 DEG C), measure above-mentioned bond strength.
Beneficial effect:
Flame retardant rubber pipe of the present invention, with Low Density Polyethylene (LLDPE), ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) and high molecular crosslink polyethylene are main raw material, science composite with rubber hose sulfuration after there is the polyimide of good adhesion performance, tetraethylenepentamine, alpha-sulfo-fatty acid alkyl ester salt, epoxy resin, SBR latex, the chemical substances such as rosin prepare inner lining film, adopt the method for simultaneously inner lining film adhesive surface and rubber hose adhesive surface being carried out to corona treatment, to strengthen its cohesiveness, and the glass steel reinforcing fiber with shielding property is compounded with at upper layer, rubber hose upper layer is made to have excellent anti-radiation, especially the potential safety hazard that the pipeline solving transfer oil and Sweet natural gas brings because of ionizing rays, a kind of inner lining film bonding of final preparation firmly, anti-radiation is strong, LPG can be carried, the flame retardant rubber pipe of LNG and severe corrosive chemical solvents, it is to X in nuclear radiation, the specific absorption of gamma-rays and various neutron can up to arriving 97.5-99.5%, the bounding force (N/25mm) of inner lining film and rubber layer reaches 160-180.Concrete 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 aminas, and with there is the sulfonated alkyl ester salt of wettability and there is the epoxy resin with rubber good adhesion, SBR latex and rosin science composite, the cohesiveness of high-molecular polythene film is improved, in maintenance Low Density Polyethylene (LLDPE), under the characteristic of ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) and the poly excellent material of high molecular crosslink, overcome the defect of its bad adhesion, described inner lining film is made to have good wear resistance, temperature tolerance, erosion resistance, oil-proofness, resistance to acids and bases, under the characteristic conditions such as self lubricity, also have excellent in performance that is rubber bound.It should be noted that, above-mentioned mechanism is the deduction of present inventor etc., even if the mechanism of the present application is not inconsistent with described mechanism, still belongs in the scope of the invention.Also it should be noted that, the above-mentioned performance of described inner lining film is composite, the synergistic effect of its each material component science, not the superposition of simple material function.In fact, described inner lining film compared with prior art really and the vulcanization of rubber bond after there is excellent adhesive property.
2. glass steel reinforcing fiber of the present invention is with reinforced plastic glass fibre silk, anti-neutron fiber yarn, anti-X, gamma-rays fiber yarn, lead powder, boron carbide powder science is composite, adopt blending, dipping and stoving process are made, not only there is light weight high-strength, anti-aging, corrosion-resistant, fire-retardant, sunshade, heat insulation, the premium propertiess such as insulation, and there is shielding fast neutron, thermal neutron and X, gamma-emitting comprehensive shielded effect, particularly steeping process adopts high-voltage pulse electric factory and office reason, make glass steel reinforcing fiber appropriateness softening, grid structure is abundanter, accelerate lead powder, the seepage velocity of boron carbide powder, enhance dipping effect, improve pickling efficiency, finally enhance the radiation-proof effect of glass steel reinforcing fiber.
3. the manufacture method of polypropylene reinforced composite of the present invention compared with prior art, have chosen the main raw material of jute as weft-knitted bi-axial fabric, can make full use of the excellent mechanical property of jute and resources advantage; And utilizing weft-knitted biax weaving method biaxially to serve as a contrast yarn woven fabric to process jute weft knitting, low in raw material price, can save production cost, the reinforcement of the environment-friendly composite material of development of new high-quality, does not produce chemical waste, environmentally safe simultaneously.Described polypropylene reinforced composite tensile strength is 104.8-112.6MPa, and flexural strength is 120.1-139.8MPa.
4. preparation method's technique of rubber hose of the present invention is simple, easy to operate; controllability is good; efficiency is high; be produced on a large scale; on the basis that existing sulfuration bonds; by carrying out corona treatment respectively to the adhesive surface of inner lining film and rubber layer; significantly improve the surface tension of inner lining film and rubber layer adhesive surface; surface tension exponential average improves 7-11mN/m; and closely; add inner lining film and the excellent material binding of rubber layer, considerably improve the stability that follow-up inner lining film and rubber layer sulfuration bond, inner lining film not easily comes off with rubber layer.
Embodiment
The present invention is described below by specific embodiment.Unless stated otherwise, technique means used in the present invention is method known in those skilled in the art.In addition, embodiment is interpreted as illustrative, but not limits the scope of the invention, and the spirit and scope of the invention only limited by claims.To those skilled in the art, under the prerequisite not deviating from essence of the present invention and scope, the various change carry out the material component in these embodiments and consumption or change also belong to protection scope of the present invention.
The high-power corona treatment used used in following examples 1-5 is produced for Nantong Sanxin Plastics Equipment Technology Co., Ltd., model: CW3060, maximum output voltage 15kV, peak power output 60kW, operating frequency 15-40KHz; Other industrial chemicals is commercial commodity.
Embodiment 1
A kind of flame retardant rubber pipe, comprise rubber hose body, described rubber hose body comprises internal layer, middle layer and upper layer from inside to outside successively;
Described internal layer is formed by sulfuration bonding by ethylene-propylene-diene monomer glue-line and inner lining film;
Described terpolymer EP rubber color is oyster white;
Described inner lining film is prepared primarily of the raw material of following parts by weight: LLDPE30 part, polyvinyl alcohol 25 parts, UHMWPE20 part, high molecular crosslink polyethylene 27 parts, polyimide 9 parts, tetraethylenepentamine 7 parts, alpha-sulfo-fatty acid alkyl ester salt 6 parts, epoxy resin 9 parts, SBR latex 5 parts, rosin 4 parts;
Described inner lining film adopts ordinary method raw material to be extruded rear blowing, stretching film forming, and inner lining film thickness is 0.42mm.
Described middle layer is bondd formed by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, polypropylene reinforced composite, fire retardant, brass-plated steel wire sulfuration;
The polypropylene reinforced composite of its quality 15% is contained in described middle layer;
The preparation method of described polypropylene reinforced composite, comprise the steps: by jute weft knitting biaxially knitted fabrics and polypropylene short fiber carry out interval laying, every layer of megila two sides is all covered with a layer polypropylene short fiber; Thermocompressor is heated to 65 DEG C, the megila of above-mentioned interval laying and polypropylene short fiber are placed on thermocompressor, be warmed up to 94 DEG C, be forced into 10MPa, pressurize is warming up to 147 DEG C, be warming up to 185 DEG C after insulation 6min, naturally cool to room temperature after heat-insulation pressure keeping 12min and namely obtain polypropylene reinforced composite;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber laying number is 9 layers, refers to that biaxially knitted fabrics and polypropylene short fiber laying number add up to 9 layers in jute weft knitting;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber mass ratio is 1:1.25.
Described upper layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, static inhibitor, glass steel reinforcing fiber sulfuration;
The color of described terpolymer EP rubber is green;
Described upper layer contains the glass steel reinforcing fiber of its quality 11%;
Described glass steel reinforcing fiber is prepared primarily of the raw material of following components by weight percent: reinforced plastic glass fibre silk 73 parts, anti-neutron fiber yarn 18 parts, anti-X, gamma-rays fiber yarn 13 parts, 12 parts, lead powder, boron carbide powder 8 parts;
The preparation method of described glass steel reinforcing fiber, comprises the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber yarn and anti-X, gamma-rays fiber yarn obtain flat fabric as parallel blending;
2) by unsaturated polyester resin, polyoxyethylene glycol and toluene according to mass ratio 100:8:2:22 Homogeneous phase mixing, make resin solution, then add lead powder, boron carbide powder wherein, stir to obtain plumbous boron resin solution;
3) by step 1) obtained flat fabric is in step 2) flood 60min in obtained plumbous boron resin solution, simultaneously at strength of electric field 30kV/cm, burst length 450 μ s, carries out pulsed electric field process under pulse-repetition 250Hz condition; Then dry and obtain glass steel reinforcing fiber;
Described oven dry is syllogic, and namely inlet section temperature 100 DEG C keeps 30 minutes, and drying section 135 DEG C keeps 40 minutes, and outlet section 85 DEG C keeps 25 minutes.
Preparation method.
The internal layer of described rubber hose, middle layer and upper layer all adopt conventional sulfuration bonding;
Wherein, for the internal layer of rubber hose, in order to strengthen the cohesiveness of inner lining film and rubber layer, respectively corona treatment being carried out to the adhesive surface of inner lining film and rubber layer, then carries out sulfuration bonding: curing temperature 155 DEG C, curing time 90min;
Described inner lining film adhesive surface corona treatment technique is: power 12kW, frequency 21KHz; Corona intensity is: 45mN/m;
Described rubber layer adhesive surface corona treatment technique is: power 14kW, frequency 23KHz; Corona intensity is: 47mN/m;
The rubber hose prepared through aforesaid method can up to 99.5% to the specific absorption of X, gamma-rays and various neutron in nuclear radiation, and the bounding force (N/25mm) of inner lining film and rubber layer reaches 180.
Embodiment 2
A kind of flame retardant rubber pipe, comprise rubber hose body, described rubber hose body comprises internal layer, middle layer and upper layer from inside to outside successively;
Described internal layer is formed by sulfuration bonding by ethylene-propylene-diene monomer glue-line and inner lining film;
Described terpolymer EP rubber color is oyster white;
Described inner lining film is prepared primarily of the raw material of following parts by weight: LLDPE20 part, polyvinyl alcohol 20 parts, UHMWPE15 part, high molecular crosslink polyethylene 22 parts, polyimide 8 parts, tetraethylenepentamine 5 parts, alpha-sulfo-fatty acid alkyl ester salt 5 parts, epoxy resin 8 parts, SBR latex 4 parts, rosin 3 parts;
Described inner lining film adopts ordinary method raw material to be extruded rear blowing, stretching film forming, and inner lining film thickness is 0.35mm.
Described middle layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, polypropylene reinforced composite, fire retardant, brass-plated steel wire sulfuration;
The polypropylene reinforced composite of its quality 10% is contained in described middle layer;
The preparation method of described polypropylene reinforced composite, comprise the steps: by jute weft knitting biaxially knitted fabrics and polypropylene short fiber carry out interval laying, every layer of megila two sides is all covered with a layer polypropylene short fiber; Thermocompressor is heated to 65 DEG C, the megila of above-mentioned interval laying and polypropylene short fiber are placed on thermocompressor, be warmed up to 92 DEG C, be forced into 8MPa, pressurize is warming up to 145 DEG C, be warming up to 180 DEG C after insulation 5min, naturally cool to room temperature after heat-insulation pressure keeping 10min and namely obtain polypropylene reinforced composite;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber laying number is 7 layers, refers to that biaxially knitted fabrics and polypropylene short fiber laying number add up to 7 layers in jute weft knitting;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber mass ratio is 1:1.2.
Described upper layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, static inhibitor, glass steel reinforcing fiber sulfuration;
The color of described terpolymer EP rubber is red;
Described upper layer contains the glass steel reinforcing fiber of its quality 10%;
Raw material primarily of the following components by weight percent preparation of described glass steel reinforcing fiber: reinforced plastic glass fibre silk 70 parts, anti-neutron fiber yarn 16 parts, anti-X, gamma-rays fiber yarn 12 parts, 10 parts, lead powder, boron carbide powder 6 parts;
The preparation method of described glass steel reinforcing fiber, comprises the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber yarn and anti-X, gamma-rays fiber yarn obtain flat fabric as parallel blending;
2) by unsaturated polyester resin, aluminium hydroxide, polyoxyethylene glycol and dimethylbenzene according to mass ratio 100:7:1:20 Homogeneous phase mixing, make resin solution, then add lead powder, boron carbide powder wherein, stir to obtain plumbous boron resin solution;
3) by step 1) obtained flat fabric is in step 2) flood 50min in obtained plumbous boron resin solution, simultaneously at strength of electric field 20kV/cm, burst length 400 μ s, carries out pulsed electric field process under pulse-repetition 200Hz condition; Then dry and obtain glass steel reinforcing fiber;
Described oven dry is syllogic, and namely inlet section temperature 90 DEG C keeps 40 minutes, and drying section 120 DEG C keeps 50 minutes, and outlet section 70 DEG C keeps 30 minutes.
Preparation method.
The internal layer of described rubber hose, middle layer and upper layer all adopt conventional sulfuration bonding;
Wherein, for the internal layer of rubber hose, in order to strengthen the cohesiveness of inner lining film and rubber layer, respectively corona treatment being carried out to the adhesive surface of inner lining film and rubber layer, then carries out sulfuration bonding: curing temperature 145 DEG C, curing time 150min;
Described inner lining film adhesive surface corona treatment technique is: power 10kW, frequency 19KHz; Corona intensity is: 43mN/m;
Described rubber layer adhesive surface corona treatment technique is: power 12kW, frequency 22KHz; Corona intensity is: 45mN/m;
The rubber hose prepared through aforesaid method can up to 99% to the specific absorption of X, gamma-rays and various neutron in nuclear radiation, and the bounding force (N/25mm) of inner lining film and rubber layer reaches 175.
Embodiment 3
A kind of flame retardant rubber pipe, comprise rubber hose body, described rubber hose body comprises internal layer, middle layer and upper layer from inside to outside successively;
Described internal layer is formed by sulfuration bonding by ethylene-propylene-diene monomer glue-line and inner lining film;
Described terpolymer EP rubber color is oyster white;
Described inner lining film is prepared primarily of the raw material of following parts by weight: LLDPE40 part, polyvinyl alcohol 30 parts, UHMWPE25 part, high molecular crosslink polyethylene 32 parts, polyimide 10 parts, tetraethylenepentamine 8 parts, alpha-sulfo-fatty acid alkyl ester salt 7 parts, epoxy resin 10 parts, SBR latex 6 parts, rosin 5 parts;
Described inner lining film adopts ordinary method raw material to be extruded rear blowing, stretching film forming, and inner lining film thickness is 0.5mm.
Described middle layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, polypropylene reinforced composite, fire retardant, brass-plated steel wire sulfuration;
The polypropylene reinforced composite of its quality 18% is contained in described middle layer;
The preparation method of described polypropylene reinforced composite, comprise the steps: by jute weft knitting biaxially knitted fabrics and polypropylene short fiber carry out interval laying, every layer of megila two sides is all covered with a layer polypropylene short fiber; Thermocompressor is heated to 65 DEG C, the megila of above-mentioned interval laying and polypropylene short fiber are placed on thermocompressor, be warmed up to 96 DEG C, be forced into 12MPa, pressurize is warming up to 148 DEG C, be warming up to 190 DEG C after insulation 8min, naturally cool to room temperature after heat-insulation pressure keeping 15min and namely obtain polypropylene reinforced composite;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber laying number is 11 layers, refers to that biaxially knitted fabrics and polypropylene short fiber laying number add up to 11 layers in jute weft knitting;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber mass ratio is 1:2.
Described upper layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, static inhibitor, glass steel reinforcing fiber sulfuration;
The color of described terpolymer EP rubber is yellow;
Described upper layer contains the glass steel reinforcing fiber of its quality 13%;
Raw material primarily of the following components by weight percent preparation of described glass steel reinforcing fiber: reinforced plastic glass fibre silk 75 parts, anti-neutron fiber yarn 20 parts, anti-X, gamma-rays fiber yarn 15 parts, 15 parts, lead powder, boron carbide powder 10 parts;
The preparation method of described glass steel reinforcing fiber, comprises the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber yarn and anti-X, gamma-rays fiber yarn obtain flat fabric as parallel blending;
2) by unsaturated polyester resin, aluminium hydroxide, polyoxyethylene glycol and toluene according to mass ratio 100:9:3:25 Homogeneous phase mixing, make resin solution, then add lead powder, boron carbide powder wherein, stir to obtain plumbous boron resin solution;
3) by step 1) obtained flat fabric is in step 2) flood 70min in obtained plumbous boron resin solution, simultaneously at strength of electric field 40kV/cm, burst length 500 μ s, carries out pulsed electric field process under pulse-repetition 300Hz condition; Then dry and obtain glass steel reinforcing fiber;
Described oven dry is syllogic, and namely inlet section temperature 110 DEG C keeps 20 minutes, and drying section 150 DEG C keeps 30 minutes, and outlet section 100 DEG C keeps 20 minutes.
Preparation method.
The internal layer of described rubber hose, middle layer and upper layer all adopt conventional sulfuration bonding;
Wherein, for the internal layer of rubber hose, in order to strengthen the cohesiveness of inner lining film and rubber layer, respectively corona treatment being carried out to the adhesive surface of inner lining film and rubber layer, then carries out sulfuration bonding: curing temperature is preferably 165 DEG C, and curing time is preferably 35min;
Described inner lining film adhesive surface corona treatment technique is: power 15kW, frequency 24KHz; Corona intensity is: 48mN/m;
Described rubber layer adhesive surface corona treatment technique is: power 16kW, frequency 25KHz; Corona intensity is: 49mN/m;
The rubber hose prepared through aforesaid method can up to 98.5% to the specific absorption of X, gamma-rays and various neutron in nuclear radiation, and the bounding force (N/25mm) of inner lining film and rubber layer reaches 170.
Embodiment 4
A kind of flame retardant rubber pipe, comprise rubber hose body, described rubber hose body comprises internal layer, middle layer and upper layer from inside to outside successively;
Described internal layer is formed by sulfuration bonding by ethylene-propylene-diene monomer glue-line and inner lining film;
Described terpolymer EP rubber color is oyster white;
Described inner lining film is prepared primarily of the raw material of following parts by weight: LLDPE20 part, polyvinyl alcohol 30 parts, UHMWPE15 part, high molecular crosslink polyethylene 32 parts, polyimide 8 parts, tetraethylenepentamine 8 parts, alpha-sulfo-fatty acid alkyl ester salt 5 parts, epoxy resin 10 parts, SBR latex 4 parts, rosin 5 parts;
Described inner lining film adopts ordinary method raw material to be extruded rear blowing, stretching film forming, and inner lining film thickness is 0.4mm.
Described middle layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, polypropylene reinforced composite, fire retardant, brass-plated steel wire sulfuration; The polypropylene reinforced composite of its quality 5% is contained in described middle layer;
The preparation method of described polypropylene reinforced composite, comprise the steps: by jute weft knitting biaxially knitted fabrics and polypropylene short fiber carry out interval laying, every layer of megila two sides is all covered with a layer polypropylene short fiber; Thermocompressor is heated to 65 DEG C, the megila of above-mentioned interval laying and polypropylene short fiber are placed on thermocompressor, be warmed up to 92 DEG C, be forced into 12MPa, pressurize is warming up to 145 DEG C, be warming up to 180 DEG C after insulation 8min, naturally cool to room temperature after heat-insulation pressure keeping 15min and namely obtain polypropylene reinforced composite;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber laying number is 9 layers, refers to that biaxially knitted fabrics and polypropylene short fiber laying number add up to 9 layers in jute weft knitting;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber mass ratio is 1:1.25.
Described upper layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, static inhibitor, glass steel reinforcing fiber sulfuration;
The color of described terpolymer EP rubber is blue;
Described upper layer contains the glass steel reinforcing fiber of its quality 8%;
Raw material primarily of the following components by weight percent preparation of described glass steel reinforcing fiber: reinforced plastic glass fibre silk 70 parts, anti-neutron fiber yarn 20 parts, anti-X, gamma-rays fiber yarn 12 parts, 15 parts, lead powder, boron carbide powder 6 parts;
The preparation method of described glass steel reinforcing fiber, comprises the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber yarn and anti-X, gamma-rays fiber yarn obtain flat fabric as parallel blending;
2) by unsaturated polyester resin, aluminium hydroxide, polyoxyethylene glycol and solvent according to mass ratio 100:7:3:20 Homogeneous phase mixing, make resin solution, then add lead powder, boron carbide powder wherein, stir to obtain plumbous boron resin solution;
Further, described solvent is toluene, dimethylbenzene 1:1 Homogeneous phase mixing in mass ratio;
3) by step 1) obtained flat fabric is in step 2) flood 60min in obtained plumbous boron resin solution, then dry and obtain glass steel reinforcing fiber;
Preparation method.
The internal layer of described rubber hose, middle layer and upper layer all adopt conventional sulfuration bonding;
Wherein, for the internal layer of rubber hose, in order to strengthen the cohesiveness of inner lining film and rubber layer, respectively corona treatment being carried out to the adhesive surface of inner lining film and rubber layer, then carries out sulfuration bonding: curing temperature 145 DEG C, curing time 35min;
Described inner lining film adhesive surface corona treatment technique is: power 10kW, frequency 24KHz; Corona intensity is: 46mN/m;
Described rubber layer adhesive surface corona treatment technique is: power 12kW, frequency 25KHz; Corona intensity is: 47mN/m;
The rubber hose prepared through aforesaid method can up to 97.5% to the specific absorption of X, gamma-rays and various neutron in nuclear radiation, and the bounding force (N/25mm) of inner lining film and rubber layer reaches 160.
Embodiment 5
A kind of flame retardant rubber pipe, comprise rubber hose body, described rubber hose body comprises internal layer, middle layer and upper layer from inside to outside successively;
Described internal layer is formed by sulfuration bonding by ethylene-propylene-diene monomer glue-line and inner lining film;
Described terpolymer EP rubber color is oyster white;
Described inner lining film is prepared primarily of the raw material of following parts by weight: LLDPE40 part, polyvinyl alcohol 20 parts, UHMWPE25 part, high molecular crosslink polyethylene 22 parts, polyimide 10 parts, tetraethylenepentamine 5 parts, alpha-sulfo-fatty acid alkyl ester salt 7 parts, epoxy resin 8 parts, SBR latex 6 parts, rosin 3 parts;
Described inner lining film adopts ordinary method raw material to be extruded rear blowing, stretching film forming, and inner lining film thickness is 0.4mm.
Described middle layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, polypropylene reinforced composite, fire retardant, brass-plated steel wire sulfuration; The polypropylene reinforced composite of its quality 30% is contained in described middle layer;
The preparation method of described polypropylene reinforced composite, comprise the steps: by jute weft knitting biaxially knitted fabrics and polypropylene short fiber carry out interval laying, every layer of megila two sides is all covered with a layer polypropylene short fiber; Thermocompressor is heated to 65 DEG C, the megila of above-mentioned interval laying and polypropylene short fiber are placed on thermocompressor, be warmed up to 92 DEG C, be forced into 12MPa, pressurize is warming up to 145 DEG C, be warming up to 180 DEG C after insulation 8min, naturally cool to room temperature after heat-insulation pressure keeping 15min and namely obtain polypropylene reinforced composite;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber laying number is 9 layers, refers to that biaxially knitted fabrics and polypropylene short fiber laying number add up to 9 layers in jute weft knitting;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber mass ratio is 1:1.25.
Described upper layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, static inhibitor, glass steel reinforcing fiber sulfuration;
The color of described terpolymer EP rubber is black;
Described upper layer contains the glass steel reinforcing fiber of its quality 15%;
Raw material primarily of the following components by weight percent preparation of described glass steel reinforcing fiber: reinforced plastic glass fibre silk 75 parts, anti-neutron fiber yarn 16 parts, anti-X, gamma-rays fiber yarn 15 parts, 10 parts, lead powder, boron carbide powder 10 parts;
The preparation method of described glass steel reinforcing fiber, comprises the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber yarn and anti-X, gamma-rays fiber yarn obtain flat fabric as parallel blending;
2) by unsaturated polyester resin, fire retardant, solidifying agent and solvent according to mass ratio 100:8:2:23 Homogeneous phase mixing, make resin solution, then add lead powder, boron carbide powder wherein, stir to obtain plumbous boron resin solution;
3) by step 1) obtained flat fabric is in step 2) flood 60min in obtained plumbous boron resin solution, then dry and obtain glass steel reinforcing fiber;
Preparation method.
The internal layer of described rubber hose, middle layer and upper layer all adopt conventional sulfuration bonding;
Wherein, for the internal layer of rubber hose, in order to strengthen the cohesiveness of inner lining film and rubber layer, carrying out corona treatment respectively, then carry out sulfuration bonding to the adhesive surface of inner lining film and rubber layer: curing temperature is 165 DEG C, curing time is 150min;
Described inner lining film adhesive surface corona treatment technique is: power 13kW, frequency 21KHz; Corona intensity is: 46mN/m;
Described rubber layer adhesive surface corona treatment technique is: power 15kW, frequency 24KHz; Corona intensity is: 48mN/m;
The rubber hose prepared through aforesaid method can up to 98% to the specific absorption of X, gamma-rays and various neutron in nuclear radiation, and the bounding force (N/25mm) of inner lining film and rubber layer reaches 172.
Embodiment 6 rubber hose inner lining film of the present invention and rubber layer cohesive strength simultaneous test
1. experimental program: with embodiment of the present invention 1-5 for test group, when other condition such as material, Processes and apparatus is identical, only inner lining film is different, and the corrosion-proof lining film best for cohesiveness forms control group 1; When other condition such as material, Processes and apparatus is identical, corona treatment inner lining film and rubber layer adhesive surface is not only adopted to form control group 2; When other condition such as material, Processes and apparatus is identical, only bonding mode changes into and adopts tackiness agent directly to bond formation control group 3; Then above-mentioned several scheme lower liner film and rubber layer cohesive strength is measured, as table 1:
2. measuring method: the bond strength of inner lining film and rubber layer measures by stripping test the value that bond strength (unit=N) in units of 25mm width obtains, namely, by inner lining film and the laminating of rubber synusia, press vulcanization 90 minutes at the temperature of 155 DEG C, make the sheet test film that 25mm is wide, use autoplotter to peel off from inner lining film with the angle of 180 degree with the sheet test film of the peeling rate of 50mm/ minute by acquisition in room temperature (23 DEG C), measure above-mentioned bond strength.
Table 1. inner lining film and rubber layer cohesive 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 is added up, to the contribution rate that inner lining film excellent adhesion of the present invention contributes is: the thin 20-28% of liner; Corona treatment 9-11%; Bonding mode 2-5%; Show: compared with prior art, the method for inner lining film of the present invention and corona treatment bonding surface is the basic reason producing remarkable bond effect, although bonding mode has certain influence to cohesive strength, not quite, can preferably sulfuration bonding bonding mode.
Embodiment 7 rubber hose shielding property test of the present invention
The rubber hose prepared with embodiment of the present invention 1-5 and the commercially available anti-corrosive rubber pipe (containing reinforced plastic glass fibre layer) with certain shielding property are subjects, and carry out the test of core spoke transmitance, concrete testing data is as table 2
Table 2
| Fast neutron transmitance | Thermal neutron transmitance | X, gamma-rays transmitance | Thermal neutron transmitance | |
| 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, although the commercially available rubber hose containing reinforced plastic glass fibre layer can absorb most of fast neutron and thermal neutron, but almost absorptive function is not had to X, gamma-rays and thermal neutron, rubber hose radiation-proof effect is poor, rubber hose prepared by the present invention has stronger anti-radiation, the specific absorption of X, gamma-rays and various neutron in nuclear radiation up to 97.5-99.5%, can be suitable as to the pipeline of transfer oil and Sweet natural gas, avoid the potential safety hazard because ionizing rays brings very much.
Embodiment 8 rubber hose quantitative measurement test of the present invention
By rubber hose prepared by the embodiment of the present invention 1, test model is got by standard, putting into massfraction is respectively the sulfuric acid of 30% and the sodium hydroxide solution of 30%, strong acid, highly basic, high temperature corrosion-resisting test are carried out, corrode 72h with this understanding, then take out style and measure physical properties index, result is as table 3:
Table 3 rubber hose Partial Physical Property test result
| Physicals | Embodiment 1 | 30% caustic soda corrosion 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 |
| Tear strength N/mm | 106.28 | 98.56 | 95.67 |
| Relative volume wear loss mm 3 | 68.33 | 70.65 | 71.48 |
| Hardness A | 86 | 85 | 84 |
| Rebound resilience % | 12 | 16 | 14 |
Above result shows: rubber hose of the present invention has excellent resistance to acids and bases, erosion resistance, wear resistance, rebound resilience, temperature tolerance and tear strength, has excellent physicals.
Claims (10)
1. a flame retardant rubber pipe, comprises rubber hose body, it is characterized in that, described rubber hose body comprises internal layer, middle layer and upper layer from inside to outside successively; Described internal layer is oil resistant, anti-corrosion layer; Described middle layer is fire-retardant, enhancement Layer; Described upper layer is antistatic, radiation protective layer.
2. flame retardant rubber pipe as claimed in claim 1, is characterized in that, described internal layer is at least bondd by sulfuration by ethylene-propylene-diene monomer glue-line and inner lining film and forms; The material of preparing of described inner lining film mainly to comprise in linear low density of polyethylene, ultrahigh molecular weight polyethylene(UHMWPE) and high molecular crosslink polyethylene one or more.
3. flame retardant rubber pipe as claimed in claim 2, it is characterized in that, described inner lining film is prepared primarily of the raw material of following parts by weight: LLDPE20-40 part, polyvinyl alcohol 20-30 part, UHMWPE15-25 part, high molecular crosslink polyethylene 22-32 part, polyimide 8-10 part, tetraethylenepentamine 5-8 part, alpha-sulfo-fatty acid alkyl ester salt 5-7 part, epoxy resin 8-10 part, SBR latex 4-6 part, rosin 3-5 part.
4. flame retardant rubber pipe as claimed in claim 1, it is characterized in that, described middle layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, polypropylene reinforced composite, fire retardant, brass-plated steel wire sulfuration; The polypropylene reinforced composite 5-30% of described middle layer at least containing its quality, preferred 10-18%.
5. flame retardant rubber pipe as claimed in claim 4, it is characterized in that, the preparation method of described polypropylene reinforced composite, comprise the steps: by jute weft knitting biaxially knitted fabrics and polypropylene short fiber carry out interval laying, every layer of megila two sides is all covered with a layer polypropylene short fiber; Thermocompressor is heated to 65 DEG C, the megila of above-mentioned interval laying and polypropylene short fiber are placed on thermocompressor, be warmed up to 92-96 DEG C, be forced into 8-12MPa, pressurize is warming up to 145-148 DEG C, be warming up to 180-190 DEG C after insulation 5-8min, naturally cool to room temperature after heat-insulation pressure keeping 10-15min and namely obtain polypropylene reinforced composite;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber laying number is 7-11 layer;
Described jute weft knitting biaxially knitted fabrics and polypropylene short fiber mass ratio is 1:1.2-2.
6. flame retardant rubber pipe as claimed in claim 1, it is characterized in that, described upper layer is bondd made by terpolymer EP rubber and Ethylene Propylene Terpolymer cord thread, static inhibitor, glass steel reinforcing fiber sulfuration; The glass steel reinforcing fiber 8-15% of described upper layer at least containing its quality, preferred 10-13%.
7. flame retardant rubber pipe as claimed in claim 6, it is characterized in that, described glass steel reinforcing fiber is prepared primarily of the raw material of following components by weight percent: reinforced plastic glass fibre silk 70-75 part, anti-neutron fiber yarn 16-20 part, anti-X, gamma-rays fiber yarn 12-15 part, lead powder 10-15 part, boron carbide powder 6-10 part;
The preparation method of described glass steel reinforcing fiber, comprises the following steps:
1) using reinforced plastic glass fibre silk as warp, anti-neutron fiber yarn and anti-X, gamma-rays fiber yarn obtain flat fabric as parallel blending;
2) by unsaturated polyester resin, fire retardant, solidifying agent and solvent according to mass ratio 100:7-9:1-3:20-25 Homogeneous phase mixing, make resin solution, then add lead powder, boron carbide powder wherein, stir to obtain plumbous boron resin solution;
3) by step 1) obtained flat fabric is in step 2) flood 50-70min in obtained plumbous boron resin solution, then dry and obtain glass steel reinforcing fiber.
8. flame retardant rubber pipe as claimed in claim 7, is characterized in that, step 3) flood while at strength of electric field 20-40kV/cm, burst length 400-500 μ s, carries out pulsed electric field process under pulse-repetition 200-300Hz condition.
9. the preparation method of flame retardant rubber pipe as described in as arbitrary in claim 1-8, the internal layer of described rubber hose, middle layer and upper layer all adopt conventional sulfuration bonding, and it is characterized in that, the adhesive surface of described internal layer inner lining film and rubber layer carries out corona treatment respectively.
10. the preparation method of flame retardant rubber pipe as claimed in claim 9, it is characterized in that, described inner lining film adhesive surface corona treatment technique is: power 10-15kW, frequency 19-24KHz; Described rubber layer adhesive surface corona treatment technique is: power 12-16kW, frequency 22-25KHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510591291.0A CN105061882A (en) | 2015-09-16 | 2015-09-16 | Flame retarding rubber hose and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510591291.0A CN105061882A (en) | 2015-09-16 | 2015-09-16 | Flame retarding rubber hose and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105061882A true CN105061882A (en) | 2015-11-18 |
Family
ID=54491420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510591291.0A Withdrawn CN105061882A (en) | 2015-09-16 | 2015-09-16 | Flame retarding rubber hose and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105061882A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108284659A (en) * | 2017-01-10 | 2018-07-17 | 赢创德固赛有限公司 | Thermoplastic composite tubing with multilayer middle layer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104010803A (en) * | 2011-12-12 | 2014-08-27 | 横滨橡胶株式会社 | Rubber/resin composite hose |
| CN104480619A (en) * | 2015-01-05 | 2015-04-01 | 天津工业大学 | Jute biaxial weft knitted fabric reinforced polypropylene composite material and manufacturing method thereof |
-
2015
- 2015-09-16 CN CN201510591291.0A patent/CN105061882A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104010803A (en) * | 2011-12-12 | 2014-08-27 | 横滨橡胶株式会社 | Rubber/resin composite hose |
| CN104480619A (en) * | 2015-01-05 | 2015-04-01 | 天津工业大学 | Jute biaxial weft knitted fabric reinforced polypropylene composite material and manufacturing method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108284659A (en) * | 2017-01-10 | 2018-07-17 | 赢创德固赛有限公司 | Thermoplastic composite tubing with multilayer middle layer |
| CN108284659B (en) * | 2017-01-10 | 2020-04-07 | 赢创运营有限公司 | Thermoplastic composite pipe with multiple intermediate layers |
| US11149879B2 (en) | 2017-01-10 | 2021-10-19 | Evonik Operations Gmbh | Thermoplastic composite pipe with multilayer intermediate lamina |
| US11982396B2 (en) | 2017-01-10 | 2024-05-14 | Evonik Operations Gmbh | Thermoplastic composite pipe with multilayer intermediate lamina |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105042219B (en) | Rubber composite soft pipe of conveying LPG, LNG and severe corrosive chemical solvent and preparation method thereof | |
| CN105065804B (en) | A kind of hose and preparation method thereof | |
| CN103264867B (en) | High temperature-resistance conveyor belt | |
| CN106827735B (en) | A kind of fire-retardant electromagnetic shielding composite material of gas defence, preparation method and product | |
| CN103144383B (en) | Ultrahigh molecular weight polyethylene composite material and manufacturing method thereof | |
| CN105443877B (en) | A kind of corrosion-resistant anti-flaming glass fiber reinforced plastics exhaust duct | |
| CN106279949A (en) | A kind of polyethylene polypropylene macromolecule composite flame-proof waterproof roll | |
| CN209119723U (en) | A kind of HDPE power pipe | |
| CN105061882A (en) | Flame retarding rubber hose and preparation method thereof | |
| CN105153517A (en) | Hose with firmly bonded liner film and preparation method thereof | |
| CN105175860A (en) | High-corrosion-resistance hose and preparation method thereof | |
| CN105156776A (en) | Hose for delivering liquefied natural gas and preparation method thereof | |
| CN105202282A (en) | Radiation-resistant rubber pipe and preparation method thereof | |
| CN105179830A (en) | High-temperature-resistant and corrosion-resistant rubber tube and preparing method thereof | |
| CN113512379A (en) | Rubber composition for nuclear power station, rubber lining material and rubber lining pipeline bonding method | |
| CN105156778A (en) | Antistatic hose and preparation method thereof | |
| CN105179827A (en) | Acid-base resistant hose and manufacturing method thereof | |
| CN105179826A (en) | Hose for delivering corrosive liquid and preparing method of hose | |
| CN109734973A (en) | A kind of high intensity oil resistant conveyer and its preparation process | |
| CN105443885B (en) | Natural gas hose material using assorted fibre as skeleton | |
| CN212107244U (en) | High-strength PE pipe | |
| CN103421252A (en) | Composite rubber material | |
| CN105482375A (en) | High-efficiency and flame-retardation glass fiber reinforced plastic composite material | |
| CN104354406A (en) | Charging pile board and preparation method thereof | |
| CN104592606A (en) | High-temperature-resistant rubber pipe for car |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20151118 |