CN1618844A - Method of raising ultra high molecular weight polyethylene processing fluidity using radiation technology - Google Patents
Method of raising ultra high molecular weight polyethylene processing fluidity using radiation technology Download PDFInfo
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- CN1618844A CN1618844A CN 200410040838 CN200410040838A CN1618844A CN 1618844 A CN1618844 A CN 1618844A CN 200410040838 CN200410040838 CN 200410040838 CN 200410040838 A CN200410040838 A CN 200410040838A CN 1618844 A CN1618844 A CN 1618844A
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Abstract
A process for preparing the high-flowability ultrahigh-molecular polyethene by irradiation includes such steps as irradiating the ultrahigh-molecular polyethene by 10-100 KGY for 10 min-100 hr for generating chain-breaking reaction, proportionally mixing it with inorganic filler, and extruding out by dual-screw extruder while granulating at 250 deg.C.
Description
One, technical field
The present invention relates to a kind of method that adopts irradiation technique to improve the ultrahigh molecular weight polyethylene(UHMWPE) processing fluidity, belong to polymer processing field.
Two, background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is the very excellent thermoplastic engineering plastic of a kind of over-all properties.It has performances such as the unrivaled shock resistance of other engineering plastics, wearability, stress crack resistant and self-lubricating, and purposes is very extensive.The molecular structure of ultrahigh molecular weight polyethylene(UHMWPE) is similar with high density polyethylene(HDPE) (HDPE), but molecular chain is very long, and viscosity-average molecular weight is generally more than 1,500,000, and weight-average molecular weight surpasses 3,000,000.Because molecular chain is very long, ultrahigh molecular weight polyethylene(UHMWPE) is very easy to chain entanglement takes place, and melt viscosity is up to 10
8Pa.s, flow rate is almost nil; In addition, the critical shear rate of ultrahigh molecular weight polyethylene(UHMWPE) melt is low, when shearing rate surpasses 0.01s
-1The time melt fracture will take place, therefore be difficult to adopt conventional extruding to be processed with injection moulding method.How to solve the processing problems of ultrahigh molecular weight polyethylene(UHMWPE) effectively, be the difficult problem that countries in the world are competitively studied always.
With ultrahigh molecular weight polyethylene(UHMWPE) and other flowability preferably resin carry out blend, to reduce melt viscosity, be to improve the mobile the most frequently used method of ultrahigh molecular weight polyethylene(UHMWPE) at present, the polymkeric substance that carries out blend with ultrahigh molecular weight polyethylene(UHMWPE) mainly contains high density polyethylene(HDPE) (HDPE), new LDPE (film grade) (LDPE), polypropylene (PP) etc.Though the ultrahigh molecular weight polyethylene(UHMWPE) chemical structure is close with other polyethylene, under general blending equipment and condition, co-mixing system is difficult to form homodisperse, layering easily in the course of processing, the crystallization separately of each component.In addition, add after the polyethylene of other kind, cause the reduction of physical and mechanical propertiess such as ultrahigh molecular weight polyethylene(UHMWPE) resistance to impact shock, wear resistance inevitably; Between the lamella of layered silicate bonding force a little less than, frictional coefficient is very little, can slide between the lamella, can improve the flowability of ultrahigh molecular weight polyethylene(UHMWPE) after the adding.But because the ultrahigh molecular weight polyethylene(UHMWPE) melt viscosity is higher, and the two polarity differs bigger, so layered silicate is not easy to be uniformly dispersed, and the mechanical property of co-mixing system worsens; The method that another kind improves the ultrahigh molecular weight polyethylene(UHMWPE) flowability is to add flow ability modifying agent.The effect of flow ability modifying agent is to promote macromolecular chain to separate to twine, and between macromole lubricate, improve molecule interchain transmission ofenergy, thereby make segment slide easily, flowability improves.Because atom is symmetric offset spread in the ultrahigh molecular weight polyethylene(UHMWPE) molecular structure, has self lubricity preferably, and the viscosity of ultrahigh molecular weight polyethylene(UHMWPE) molten state is very high, stick on the processing units easily, lubricated outside only plaing a part when therefore the lubricant applications that polyethylene is commonly used is to ultrahigh molecular weight polyethylene(UHMWPE), the long-chain that makes ultrahigh molecular weight polyethylene(UHMWPE) twines and melt-flow adding comparatively fast to separate man-hour, also needs to add other component additive, this method more complicated.The processing of ultrahigh molecular weight polyethylene(UHMWPE) is a global difficult problem always.
Chinese patent 1191230A is disclosed to be the preparation method who extrudes with the injection grade super-high molecular weight polyethylene PP Pipe Compound, this method is liquid crystal polymer, antioxidant and the additive that adds certainweight per-cent in ultrahigh molecular weight polyethylene(UHMWPE), carry out the co-blended after drying, produce at last and can be directly used in the ultrahigh molecular weight polyethylene(UHMWPE) PP Pipe Compound of extruding and injecting.By the content of this patent disclosure as can be known, the prescription of this PP Pipe Compound is complicated.
Chinese patent 245179A is disclosed to be the ultra-high molecular weight polyvinyl composite that a kind of available extrusion molding is processed.It is by 100～4,000,000 ultrahigh molecular weight polyethylene(UHMWPE)s, naphthane, low molecular weight polyethylene, amides lubricant and nanometer grade silica or aluminium sesquioxide under 60 ± 5 ℃, mix.By the content of this patent disclosure as can be known, the prescription of said composition is complicated.
Three, summary of the invention
The objective of the invention is provides a kind of irradiation technique to improve the method for ultrahigh molecular weight polyethylene(UHMWPE) processing fluidity at the deficiencies in the prior art, be characterized in ultrahigh molecular weight polyethylene(UHMWPE) is carried out irradiation, make the chain rupture of ultrahigh molecular weight polyethylene(UHMWPE) molecule appropriateness, molecular weight slightly reduces, molecular entanglement weakens, introduce on the molecular chain and contain the oxygen polar group, improve the consistency of ultrahigh molecular weight polyethylene(UHMWPE) and mineral filler co-mixing system, on the basis that does not affect the mechanical properties, improve the flowability of ultrahigh molecular weight polyethylene(UHMWPE).
Purpose of the present invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1. the irradiation of ultrahigh molecular weight polyethylene(UHMWPE)
At room temperature in the air ultrahigh molecular weight polyethylene(UHMWPE) is carried out irradiation, irradiation dose is 10～100kGy, and irradiation time is 10 minutes～100 hours.Make ultrahigh molecular weight polyethylene(UHMWPE) generation chain-breaking reaction, molecular weight reduces, and molecular entanglement weakens, and introduces oxy radical on the molecular chain.
2. the blend of irradiated ultrahigh molecular weight polyethylene and mineral filler
With irradiated ultrahigh molecular weight polyethylene 100 weight parts and mineral filler 1～10 weight part, after mixing in the adding high-speed mixer, use twin screw extruder, be respectively 230～250 ℃, 230～250 ℃, 230～250 ℃, 230～250 ℃ in temperature, 230～250 ℃ of extruding pelletizations of head temperature, the superhigh molecular weight polyethylene material of the processing fluidity that has been improved.
Mineral filler is any in talcum, mica, kaolin or the glass microballon,
The present invention has following advantage: technology is simple, and is easy and simple to handle, and cost is lower, and the ultrahigh molecular weight polyethylene(UHMWPE) of modification has excellent comprehensive performances, detailed being shown in Table 1.
Four, embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment:
1. at room temperature in the air, adopt JJ-2 type electrostatic accelerator that ultrahigh molecular weight polyethylene(UHMWPE) is carried out irradiation, irradiation dose is 80kGy, and irradiation time is 13.3 minutes.Again irradiated ultrahigh molecular weight polyethylene 10kg and mica 0.5kg are added after high-speed mixer mixes, use the twin screw extruder extruding pelletization, each section temperature is respectively 220 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃ of head temperatures, the ultra-high-molecular-weight polyethylene material of the processing fluidity that has been improved.
2. at room temperature in the air, adopt right cylinder formula Co
60Gamma ray projector carries out irradiation to ultrahigh molecular weight polyethylene(UHMWPE), irradiation dose is 50kGy, irradiation time is 50 hours, again irradiated ultrahigh molecular weight polyethylene 10kg and talcum 0.15kg are added after high-speed mixer mixes, use the twin screw extruder extruding pelletization, each section temperature is respectively 220 ℃, 240 ℃, 240 ℃, 240 ℃, 240 ℃ of head temperatures, the ultra-high-molecular-weight polyethylene material of the processing fluidity that has been improved.
3. at room temperature in the air, adopt right cylinder formula Co
60Gamma ray projector carries out irradiation to ultrahigh molecular weight polyethylene(UHMWPE), and irradiation dose is 100kGy, and irradiation time is 100 hours.Again irradiated ultrahigh molecular weight polyethylene 10kg and kaolin 0.9kg are added after high-speed mixer mixes, use the twin screw extruder extruding pelletization, each section temperature is respectively 220 ℃, 235 ℃, 235 ℃, 235 ℃, 235 ℃ of head temperatures, the ultra-high-molecular-weight polyethylene material of the processing fluidity that has been improved.
Table 1 adopts the performance of the ultrahigh molecular weight polyethylene(UHMWPE) of modification of the present invention
Tensile yield strength Izod notched Izod impact strength elongation at break melt flow rate (MFR)
*
Sample
(MPa) (J/m) (％) (g/10min)
Ultrahigh molecular weight polyethylene(UHMWPE)-＞1,000 364 0
Modification of the present invention-1 26.0＞1,000 597 0.37
Modification of the present invention-2 28.5＞1000＞900 0.4
Modification of the present invention-3 28.7＞1000＞900 0.5
Modification of the present invention-4 31.1＞1,000 346 1.14
*The melt flow rate (MFR) test condition: probe temperature is 250 ℃, and load is 10kg.
Claims (2)
1. irradiation technique improves the method for ultrahigh molecular weight polyethylene(UHMWPE) processing fluidity, it is characterized in that:
(1) irradiation of ultrahigh molecular weight polyethylene(UHMWPE)
At room temperature in the air ultrahigh molecular weight polyethylene(UHMWPE) is carried out irradiation, irradiation dose is 10～100kGy, and irradiation time is 10 minutes～100 hours.Make ultrahigh molecular weight polyethylene(UHMWPE) generation chain-breaking reaction, molecular weight reduces, and molecular entanglement weakens, and introduces oxy radical on the molecular chain,
(2) blend of irradiated ultrahigh molecular weight polyethylene and mineral filler
After mixing in irradiated ultrahigh molecular weight polyethylene 100 weight parts and mineral filler 1～10 weight part adding high-speed mixer, use twin screw extruder, be respectively 230～250 ℃, 230～250 ℃, 230～250 ℃, 230～250 ℃ in temperature, 230～250 ℃ of extruding pelletizations of head temperature, the superhigh molecular weight polyethylene material of the processing fluidity that has been improved.
2. improve the method for ultrahigh molecular weight polyethylene(UHMWPE) processing fluidity according to the described irradiation technique of claim 1, it is characterized in that mineral filler is any in talcum, mica, kaolin or the glass microballon.
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| CN 200410040838 CN1256368C (en) | 2004-10-14 | 2004-10-14 | Method of raising ultra high molecular weight polyethylene processing fluidity using radiation technology |
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| CN 200410040838 CN1256368C (en) | 2004-10-14 | 2004-10-14 | Method of raising ultra high molecular weight polyethylene processing fluidity using radiation technology |
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| CN1256368C CN1256368C (en) | 2006-05-17 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273278A (en) * | 2014-07-18 | 2016-01-27 | 新乐市鑫客隆塑业有限公司 | Plastic material formula |
| CN108611006A (en) * | 2016-12-19 | 2018-10-02 | 上海海优威新材料股份有限公司 | Caking property protective film of cross-linking radiation and preparation method thereof |
| CN109161985A (en) * | 2018-07-28 | 2019-01-08 | 安徽省义顺渔网渔具有限公司 | A kind of high intensity is resistance to sting high-performance fishing lines |
| CN109537075A (en) * | 2018-11-20 | 2019-03-29 | 石狮市川大先进高分子材料研究中心 | Method by irradiation-induced degradation ultra-high molecular weight polyethylene surface molecules and its application in melt spinning |
| CN111571855A (en) * | 2020-06-02 | 2020-08-25 | 中广核中科海维科技发展有限公司 | Method for improving melt index of polypropylene plastic particles through irradiation |
| CN113461953A (en) * | 2021-06-16 | 2021-10-01 | 济南大学 | Preparation method of polychlorotrifluoroethylene resin |
-
2004
- 2004-10-14 CN CN 200410040838 patent/CN1256368C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273278A (en) * | 2014-07-18 | 2016-01-27 | 新乐市鑫客隆塑业有限公司 | Plastic material formula |
| CN108611006A (en) * | 2016-12-19 | 2018-10-02 | 上海海优威新材料股份有限公司 | Caking property protective film of cross-linking radiation and preparation method thereof |
| CN109161985A (en) * | 2018-07-28 | 2019-01-08 | 安徽省义顺渔网渔具有限公司 | A kind of high intensity is resistance to sting high-performance fishing lines |
| CN109537075A (en) * | 2018-11-20 | 2019-03-29 | 石狮市川大先进高分子材料研究中心 | Method by irradiation-induced degradation ultra-high molecular weight polyethylene surface molecules and its application in melt spinning |
| CN111571855A (en) * | 2020-06-02 | 2020-08-25 | 中广核中科海维科技发展有限公司 | Method for improving melt index of polypropylene plastic particles through irradiation |
| CN113461953A (en) * | 2021-06-16 | 2021-10-01 | 济南大学 | Preparation method of polychlorotrifluoroethylene resin |
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| CN1256368C (en) | 2006-05-17 |
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