CN101824180A - High elasticity polyolefin hose with radiation crosslinking and preparation method thereof - Google Patents
High elasticity polyolefin hose with radiation crosslinking and preparation method thereof Download PDFInfo
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- CN101824180A CN101824180A CN 201010173811 CN201010173811A CN101824180A CN 101824180 A CN101824180 A CN 101824180A CN 201010173811 CN201010173811 CN 201010173811 CN 201010173811 A CN201010173811 A CN 201010173811A CN 101824180 A CN101824180 A CN 101824180A
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- radiation crosslinking
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Abstract
The invention discloses a high elasticity polyolefin hose with radiation crosslinking, wherein the high elasticity polyolefin hose is prepared by extruding a blend of polyethylene, polyolefin elastomer and rubber through a tube extruding machine and radiating by electronic rays; the blend thereof comprises the compositions in percentage by weight: 30-60 percent of the polyethylene, 20-40 percent of the polyolefin elastomer and 20-40 percent of the rubber. Through radiation crosslinking treatment, the high temperature resistance use performance of the high elasticity polyolefin hose is obviously enhanced; compared with an ordinary hose, no chemical cross-linking agent is added in the polyolefin hose production process, and a product can be completely used in a field of drinking water.
Description
Technical field
The present invention relates to polyolefine (P0-Xc) flexible pipe of a kind of elastomeric radiation crosslinking and preparation method thereof; More particularly, the present invention relates to utilize the polyolefin hose and preparation method thereof of the radiation crosslinking that electron irradiation produces.
Background technology
The prescription of present similar flexible pipe mostly is gum (being generally EPDM, i.e. terpolymer EP rubber) or PVC, and wherein rubber hose vulcanizes after extrusion moulding again, and the PVC flexible pipe then is that polyvinyl chloride resin is sneaked into directly extrusion moulding behind the various auxiliary agents.
For example, Chinese patent 02132289.9 discloses a kind of to low-pollution hose that portion's mobile fluid contamination degree is low and the rubber combination that is used for this flexible pipe within it.The low-pollution hose of this patent is to be made of as rubber combination that must composition the weighting agent that is laminate structure with rubber, peroxide vulcanizing agent and crystalline structure, wherein, rubber is to be made of at least a kind of material in ethylene-propylene-diene terpolymer, ethylene-propylene copolymer and the polysiloxane rubber.
Chinese patent application 02132288.0 discloses a kind of flexible pipe, and it is to have by the rubber layer that constitutes as rubber combination that must composition with following (A)-(D), and the flexible pipe of the rhythmo structure of the laminate layers that is made of tinsel and resin: (A) by at least a kind in ethylene-propylene-diene terpolymer and ethylene-propylene copolymer rubber that constitutes; (B) peroxide vulcanizing agent; (C) Resorcinol based compound; (D) melamine resin.That the disclosed flexible pipe of this patent application has is in light weight, cost is low, and barrier properties for gases is good.
Chinese patent application 96116055.1 discloses a kind of PVC high pressure hose and base material, can be used as the fluid hose of pressure requirement, it adopts polyvinyl chloride, phthalic acid two (2, ethyl) own ester, tribasic lead sulfate, dibasic Lead Phosphite, calcium stearate, stearic acid, add permanent yellow again, white dyes is made the flexible pipe base material, between interior pipe in the flexible pipe, the enhancement layer layer of adhesive is arranged, between enhancement layer and outer tube, layer of adhesive is arranged.The alternative rubber hose of PVC high pressure hose of this patent application.
Chinese patent application 200510056543.6 discloses a kind of heat-resistant hose that also shows good interlayer connectivity under hot environment.This heat-resistant hose has with containing the internal layer (containing fluororubber layer 1) that viton forms, stromatolithic structure with the acrylic rubber glue-line 2 that forms in its periphery, aforesaid propylene acid rubber layer 2 is by forming as rubber combination that must composition with following (A)-(D), (A) acrylic elastomer, (B) peroxide cross-linking agent, (C) thiodiphenylamine (D) is subjected to sour agent.
Chinese patent application 200710137583.2 discloses a kind of nano material modified PVC water transfer hosetube, and it contains the component of following umber: polyvinyl chloride resin 100 weight parts, softening agent 15-40 weight part, lubricant 0.2-1.5 weight part, processing aid 0.5-3 weight part, thermo-stabilizer 1-3 weight part, coupling agent 0.1-0.8 weight part, nano-calcium carbonate 5-20 weight part, carbon black 0.5-1.5 weight part.The advantage of this delivery hose is: burstpressures and tensile strength height mainly are applicable to the farmland water-saving irrigation.
Chinese patent application 200910099573.3 discloses a kind of environment-friendly water-supply hose with antibacterial, and its material comprises polyvinyl chloride resin, softening agent, thermo-stabilizer, inorganic organic composite antibiotic agent and lubricant, and the mean polymerisation degree of polyvinyl chloride resin is 900-1300.The mass ratio of each component is: polyvinyl chloride resin: 100 parts; Softening agent: 40～70 parts; Thermo-stabilizer: 2～4 parts; Inorganic organic composite antibiotic agent: 0.1～0.4 part; Lubricant: 0.2～0.6 part; Each component and the mass ratio thereof of inorganic organic composite antibiotic agent are: tourmaline powder: 90-120 part; Zinc oxide: 20-35 part; Nanometer silver: 10-20 part; Zeolite powder: 45-55 part; 2,4,4 '-three chloro-2 '-dihydroxy diphenyl ether 10-15 part.It is good that the disclosed flexible pipe of this application has better anti-bacterial effect.
But,, still, all can't have good flexibility and high strength concurrently based on the flexible pipe of PVC no matter be flexible pipe based on rubber; And along with domestic and international environmental protection cry is surging, elastic hose raw materials such as PVC will step down from the stage of history certainly, and the gum goods also can be replaced by composite rubber-plastic material.
The braided steel wire enhancement type of now selling on the market or terylene woven enhancement type connect flexible pipe flexible liner pipe and mostly are EPDM or PVC material produce, exist many drawbacks from sanitation performance, life-time service life-span, the high temperature resistant degree of product of product.
Therefore, be necessary to provide a kind of flexible pipe novel, that have elasticity and intensity concurrently.
Summary of the invention
One of purpose of the present invention provides a kind of novel flexible pipe, is the flexible pipe of major ingredient and is the flexible pipe of major ingredient with PVC replacing in the prior art with EPDM.
Another object of the present invention provides a kind of method for preparing above-mentioned new-type of hose.
On the one hand, for realizing above-mentioned goal of the invention, the invention provides a kind of polyolefin hose of elastomeric radiation crosslinking, wherein, this polyolefin hose is that the blend by polyethylene, polyolefin elastomer and rubber is squeezed into pipe by tube extruding machine, and then radiation obtains through electron rays; In weight percentage, the content that changes polyethylene in the blend, polyolefin elastomer and rubber is:
Polyethylene 30-60%
Polyolefin elastomer 20-40%
Rubber 20-40%.
Preferably, in the polyolefin hose of above-mentioned radiation crosslinking, in weight percentage, the content of polyethylene, polyolefin elastomer and rubber is in the blend:
Polyethylene 40-60%
Polyolefin elastomer 20-30%
Rubber 20-40%.
In the polyolefin hose of radiation crosslinking of the present invention, adopt the co-mixing system of polyethylene, polyolefin elastomer (POE), three kinds of raw materials of rubber, test-results shows that the snappiness polyolefine radiation crosslinking pipe flexibility aspect that produces with this prescription can reach the index of pure EPDM pipe or soft pvc pipe fully, and its tubing intensity also is better than pure EPDM pipe.
Preferably, in the polyolefin hose of radiation crosslinking of the present invention, polyethylene can adopt HDPE, MDPE, LDPE, its mixture etc., the preferred use hanged down high density polyethylene(HDPE) (LDPE), linear low density polyethylene (LLDPE), and rubber can adopt terpolymer EP rubber (EPDM) or styrene-butadiene rubber(SBR).
Among the present invention, on the basis that guarantees the tubing flexibility, can adopt the higher LDPE of intensity index, POE, the EPDM raw material trade mark, with the intensity of further raising tubing, guarantee simultaneously that whole formula system has that Costco Wholesale is cheap, have good intermiscibility between each component, processing characteristics is simple and convenient.
From processing characteristics, simple EPDM or POE processing characteristics are relatively poor, and the difficult high-speed and continuous that realizes is extruded, and the LDPE processing characteristics is very excellent.The present invention adopts three component co-mixing systems, and processing characteristics also is better than simple EPDM greatly.
Further, in the polyolefin hose of radiation crosslinking of the present invention,, can further contain the oxidation inhibitor of 0.2-2% in weight percentage.Oxidation inhibitor has no special requirements, and can be the oxidation inhibitor of phenols, as 1010,702, can be the oxidation inhibitor of phosphorous acid esters also, as 168.
In addition, by electron irradiation, in the polyolefin hose of radiation crosslinking of the present invention, its gel fraction can be controlled at 80-90%.Test finds that along with the rising of irradiation dose, gel fraction also constantly raises, and 20 ℃ of burstpressuress remain unchanged substantially, and 95 ℃ of burstpressuress are fallen after rising.As seen, radiation crosslinking has improved the high-temperature behavior of product.
On the other hand, in order to realize purpose of the present invention, the present invention also provides a kind of method for preparing the polyolefin hose of above-mentioned radiation crosslinking, and this method comprises the steps:
A) with polyethylene, polyolefin elastomer and blend rubber granulation;
B) blend that obtains after the granulation in the steps A is squeezed into pipe by tube extruding machine;
C) adopt the electron rays radiation to make the tubing that obtains among the step B carry out cross-linking radiation.
In the method for preparing polyolefin hose of the present invention, unit mass tubing is preferably 60-100Kgy to the radiating absorption dose among the step C, and irradiation speed is preferably 100-200m/min, 100-120m/min more preferably.Test finds that gel fraction raises along with the rising of irradiation dose, but when dosage acquires a certain degree after because this component of EPDM begins to degrade, can cause the final performance of product to begin decline.
In the method for preparing polyolefin hose of the present invention, in weight percentage, the blend ratio of polyethylene, polyolefin elastomer and rubber is in the steps A: polyethylene 30-60%, polyolefin elastomer 20-40%, rubber 20-40%, preferred blend ratio is polyethylene 40-60%, polyolefin elastomer 20-30%, rubber 20-40%.
In the method for preparing polyolefin hose of the present invention, the granulation process of steps A will guarantee that three components are uniformly dispersed as much as possible, because rubber (EPDM) component intensity is too low, Kai Zeyi causes product local location intensity not up to standard if disperse not in whole system, so, aspect equipment, should dispose the twin screw extruder of big L/D ratio as far as possible; Next is to resolve the pelletizing problem.
In the method for preparing polyolefin hose of the present invention, adopt and squeeze pipe, the crosslinked mode of production in back earlier, tubing is extruded production rate can reach the 20-30m/min production rate, and cross-linking radiation speed can reach more than the 200m/min, the production efficiency height.
Common EPDM pipe or PVC flexible pipe product are short work-ing life, particularly use to be easy to break under hot conditions and leak, and polyolefin hose of the present invention is handled owing to the process radiation crosslinking, thereby its high temperature resistant use properties obviously improves; Compare with conventional hoses, do not add any chemical cross-linking agent in the polyolefin hose production process of the present invention, do not have any pungency peculiar smell, product fully can be in the use in relating to the tap water field, and sanitation performance is very superior; In addition, compare with existing Polyurethane (about 40000 yuan/ton of PU raw material) tracheae, snappiness polyolefine radiation crosslinking pipe of the present invention has cheap advantage.
Aspect prepared, to compare with traditional chemically crosslinked mode, radiation crosslinking process of the present invention is carried out under normal temperature condition, and it is crosslinked not need high temperature to cause, and production process is more energy-conservation.In addition, the present invention adopts and squeezes pipe, the crosslinked processing method in back earlier, and the speed that tubing is extruded and the speed of cross-linking radiation can be very high, thereby greatly improved the production efficiency height.
Below in conjunction with embodiment, further specify the present invention, but the present invention is not limited to these concrete embodiments, any on essence spirit of the present invention improvement or substitute, still belong to scope required for protection in claims of the present invention.
Description of drawings
Fig. 1 is the variation with electron irradiation dosage, the high temperature resistant variation of temperature curve of LDPE, POE, EPDM.
Embodiment
Employed electron irradiation equipment is 3MeV/40mA " nanometer " the type rumbatron of Chinese Academy of Sciences's Shanghai Applied Physics Research Institute among the present invention, and it has many characteristics such as energy height, line be big.The 3MeV energy can guarantee that ray has enough penetration powers, radiation product broad covered area; The 40mA line can effectively reduce irradiation time, enhances productivity.
Squeeze 2 in the production plant area of pipe among the present invention, be furnished with many of high speed pipe production lines such as German Battenfeld, Switzerland Maillefer, and it is reliable with the steady quality of guaranteeing tubing to have disposed the online wall thickness external diameter of Britain's Bellstar ultrasonic wave supervisory system on production line.
Fig. 1 has shown the variation with electron irradiation dosage, the high temperature resistant variation of temperature curve of LDPE, POE, EPDM.As can see from Figure 1, the high temperature resistant temperature of LDPE, POE increased with the increase of electron irradiation dosage before this, and was basicly stable afterwards; And that the high temperature resistant temperature of EPDM changes with the increase of electron irradiation dosage is little, just slightly increase, and if irradiation dose too high, its high temperature resistant temperature descends on the contrary.
Embodiment 1
Adopt LDPE, POE, EPDM to carry out granulation after the blend, wherein, in weight percentage, the component of LDPE is 40%, and the component of POE is 30%, and the component of EDPM is 30%.Blend extrudes through single screw rod that to make wall thickness be 1.5mm, and external diameter is the flexible pipe of 11mm, and (6～12M) carry out irradiation to flexible pipe, make high-elastic cross-linking radiation pipe of the present invention under the condition of doses.Wherein, through measuring, the mechanical property of ternary blends is:
Ultimate load (N): 222.35
The anti-intensity (MPa) of stretching: 15.78
Young's modulus (MPa): 0.75
Yield strength (MPa): 5.3
Elongation at break (%): 883.4
Breaking tenacity (MPa): 15.78
It is 1.2MPa that the irradiation flexible pipe of present embodiment is measured the maximum stress that can bear through hydraulic pressure instant blasting test (GB/T 5563-1994).
The gel fraction of the irradiation flexible pipe of present embodiment is 84.2%.
Embodiment 2
Experimental technique is with embodiment 1, but when adopting LDPE, POE, EPDM to carry out after the blend granulation, in weight percentage, the component of LDPE is 30%, and the component of POE is 40%, and the component of EDPM is 30%.
Embodiment 3
Experimental technique is with embodiment 1, but when adopting LDPE, POE, EPDM to carry out after the blend granulation, in weight percentage, the component of LDPE is 50%, and the component of POE is 30%, and the component of EDPM is 20%.
Embodiment 4
Experimental technique is with embodiment 1, but when adopting LDPE, POE, EPDM to carry out after the blend granulation, in weight percentage, the component of LDPE is 60%, and the component of POE is 20%, and the component of EDPM is 20%.
Embodiment 5
Experimental technique is with embodiment 1, but when adopting LDPE, POE, EPDM to carry out after the blend granulation, in weight percentage, the component of LDPE is 40%, and the component of POE is 20%, and the component of EDPM is 40%.
Embodiment 6
Experimental technique is with embodiment 1, but when adopting LDPE, POE, EPDM to carry out after the blend granulation, in weight percentage, the component of LDPE is 50%, and the component of POE is 25%, and the component of EDPM is 25%.
Claims (10)
1. the polyolefin hose of an elastomeric radiation crosslinking, wherein, described polyolefin hose is that the blend by polyethylene, polyolefin elastomer and rubber is squeezed into pipe by tube extruding machine, and then radiation obtains through electron rays; In weight percentage, the content of polyethylene, polyolefin elastomer and rubber is in the described blend:
Polyethylene 30-60%
Polyolefin elastomer 20-40%
Rubber 20-40%.
2. the polyolefin hose of radiation crosslinking as claimed in claim 1, wherein, in weight percentage, the content of polyethylene, polyolefin elastomer and rubber is in the described blend:
Polyethylene 40-60%
Polyolefin elastomer 20-30%
Rubber 20-40%.
3. the polyolefin hose of radiation crosslinking as claimed in claim 1 or 2, wherein, described polyethylene is high density polyethylene(HDPE), medium-density polyethylene, low high density polyethylene(HDPE) or its mixture.
4. the polyolefin hose of radiation crosslinking as claimed in claim 1 or 2, wherein, described rubber is terpolymer EP rubber or styrene-butadiene rubber(SBR).
5. the polyolefin hose of radiation crosslinking as claimed in claim 1 or 2 wherein, in weight percentage, further contains the oxidation inhibitor of 0.2-2% in the described polyolefin hose.
6. the polyolefin hose of radiation crosslinking as claimed in claim 1 or 2, wherein, the gel fraction of described polyolefin hose is 80-90%.
7. method for preparing as the polyolefin hose of one of claim 1-6 described radiation crosslinking, wherein, described method comprises the steps:
A) with polyethylene, polyolefin elastomer and blend rubber granulation;
B) blend that obtains after the granulation in the steps A is squeezed into pipe by tube extruding machine;
C) adopt the electron rays radiation to make the tubing that obtains among the step B carry out cross-linking radiation.
8. the method for preparing polyolefin hose as claimed in claim 7, wherein, in described step C, unit mass tubing is 60-100Kgy to the radiating absorption dose, irradiation speed is 100-120m/min.
9. as claim 7 or the 8 described methods that prepare polyolefin hose, wherein, in described steps A, in weight percentage, the ratio of described polyethylene, polyolefin elastomer and rubber is:
Polyethylene 30-60%
Polyolefin elastomer 20-40%
Rubber 20-40%.
10. the method for preparing polyolefin hose as claimed in claim 9, wherein, in described steps A, in weight percentage, the ratio of described polyethylene, polyolefin elastomer and rubber is:
Polyethylene 40-60%
Polyolefin elastomer 20-30%
Rubber 20-40%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010101738113A CN101824180B (en) | 2010-05-17 | 2010-05-17 | High elasticity polyolefin hose with radiation crosslinking and preparation method thereof |
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| CN2010101738113A CN101824180B (en) | 2010-05-17 | 2010-05-17 | High elasticity polyolefin hose with radiation crosslinking and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408605A (en) * | 2011-08-30 | 2012-04-11 | 吴江市远大聚合材料贸易有限公司 | Environmentally-friendly sanitary water contact hose and production method thereof |
| CN102775620A (en) * | 2012-07-10 | 2012-11-14 | 东华大学 | Preparation method for organic-inorganic hybrid polyolefin elastomer irradiation cross-linking system |
| CN102786763A (en) * | 2012-06-04 | 2012-11-21 | 上海日杰弹性体塑胶有限公司 | Flexible pipe material for temperature resistant and thermoplastic elastomer and preparation method thereof |
| CN103644396A (en) * | 2013-11-26 | 2014-03-19 | 宁波诗兰姆汽车零部件有限公司 | Cleaning pipe of automobile head lamp |
| CN104558752A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Polyethylene resin composition for gas pipe warning panel as well as manufacturing method and gas pipe warning panel |
| CN105670087A (en) * | 2016-04-11 | 2016-06-15 | 叶青 | Environment-friendly and weather-resistant polyethylene pipe |
| CN116817039A (en) * | 2023-08-30 | 2023-09-29 | 山东一泰液压科技有限公司 | Corrosion-resistant fracturing hose and preparation method thereof |
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| EP1674513A1 (en) * | 2004-12-23 | 2006-06-28 | REHAU AG + Co | TPV-Alternative |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408605A (en) * | 2011-08-30 | 2012-04-11 | 吴江市远大聚合材料贸易有限公司 | Environmentally-friendly sanitary water contact hose and production method thereof |
| CN102408605B (en) * | 2011-08-30 | 2014-03-05 | 吴江市远大聚合材料贸易有限公司 | Environmentally-friendly sanitary water contact hose and production method thereof |
| CN102786763A (en) * | 2012-06-04 | 2012-11-21 | 上海日杰弹性体塑胶有限公司 | Flexible pipe material for temperature resistant and thermoplastic elastomer and preparation method thereof |
| CN102775620A (en) * | 2012-07-10 | 2012-11-14 | 东华大学 | Preparation method for organic-inorganic hybrid polyolefin elastomer irradiation cross-linking system |
| CN102775620B (en) * | 2012-07-10 | 2014-01-29 | 东华大学 | Preparation method for organic-inorganic hybrid polyolefin elastomer irradiation cross-linking system |
| CN104558752A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Polyethylene resin composition for gas pipe warning panel as well as manufacturing method and gas pipe warning panel |
| CN103644396A (en) * | 2013-11-26 | 2014-03-19 | 宁波诗兰姆汽车零部件有限公司 | Cleaning pipe of automobile head lamp |
| CN103644396B (en) * | 2013-11-26 | 2016-06-08 | 宁波诗兰姆汽车零部件有限公司 | Vehicle headlamp cleaning pipe |
| CN105670087A (en) * | 2016-04-11 | 2016-06-15 | 叶青 | Environment-friendly and weather-resistant polyethylene pipe |
| CN116817039A (en) * | 2023-08-30 | 2023-09-29 | 山东一泰液压科技有限公司 | Corrosion-resistant fracturing hose and preparation method thereof |
| CN116817039B (en) * | 2023-08-30 | 2023-11-17 | 山东一泰液压科技有限公司 | Corrosion-resistant fracturing hose and preparation method thereof |
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| CN101824180B (en) | 2011-11-23 |
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Owner name: FOSHAN FSPG HI-TECH. SHARES CO., LTD. Free format text: FORMER NAME: FOSHAN PLASTIC GROUP CO., LTD. |
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Address after: 528000 Fenjiang Middle Road, Chancheng District, Guangdong, China, No. 85, No. Patentee after: FSPG Hi-Tech Co., Ltd. Address before: 528000 Fenjiang Middle Road, Chancheng District, Guangdong, China, No. 85, No. Patentee before: Foshan Plastic Group Co., Ltd. |