CN1478811A - Super high molecular weight polyethylene blend capable of using in extrusion processing and its processing method - Google Patents
Super high molecular weight polyethylene blend capable of using in extrusion processing and its processing method Download PDFInfo
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- CN1478811A CN1478811A CNA021336741A CN02133674A CN1478811A CN 1478811 A CN1478811 A CN 1478811A CN A021336741 A CNA021336741 A CN A021336741A CN 02133674 A CN02133674 A CN 02133674A CN 1478811 A CN1478811 A CN 1478811A
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Abstract
An ultrahigh-molecular polyethylene mixture used for extruding out is prepared from ultrahigh-molecular polyethylene, polypropylene, antioxidizing agent, nucleator and additive through proportional mixing and single-screw extruding out while applying ultrasonic vibration. Its advantages are high extruding-out efficiency and high performance.
Description
One, technical field
The present invention relates to a kind of super high molecular weight polyethylene blend and working method thereof, belong to polymer processing field.
Two, background technology
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is a kind of engineering plastics with excellent comprehensive physical and mechanical properties, has common polythene and other engineering plastics incomparable wear resistance, erosion resistance, shock-resistance and resistance to low temperature.But because its molecular weight is very big, molecule interchain entanglement degree height makes that its melt viscosity is high, and melt flow index is almost nil.This causes the difficulty of processing of UHMWPE very big, can't use common extruding or injection molding forming method processing, and the production of UHMWPE goods is still based on compacting-sintering method at present, and efficient is very low, and this has seriously restricted its range of application.
A kind of approach that solves a ultrahigh molecular weight polyethylene(UHMWPE) processing difficult problem is to use the mechanical means of particular design, reported a kind of ultrahigh molecular weight polyethylene(UHMWPE) single screw extrusion machine as Chinese patent 95219311, be characterized in that the metering zone of compression section, metering zone and screw rod at machine barrel is provided with pin; Adopt the four-part form screw rod, lower and unequal two sections of compression ratio are made in the compression section, and feeding section adopts the two start screw structure; In the screw rod exit, screen plate is set before the molding die; The groove of machine barrel feeding section adopts edge kerve nested structure.The mixing homo-effect has been strengthened in such design, has improved the latch up phenomenon of material in machine barrel feeding section and compression section, has improved the charging ability, thereby has realized that quality of item is reliable, the extruding continuously of stable yield.Its shortcoming be involving great expense of equipment and relatively poor to the adaptability of the raw material of the different varieties trade mark, Jia Gong efficient is not significantly improved simultaneously, therefore this method is not used widely.Another kind of approach is that the flowability of UHMWPE is improved, as with middle low molecular weight polyethylene or with lubricant or with the high molecule liquid crystal blending and modifying, make that UHMWPE can be with special-purpose forcing machine and injection moulding machine moulding under gentle relatively condition:
United States Patent (USP) 4281070, Japanese Patent 60240748A, 57177037 have been reported the method with UHMWPE and middle low molecular weight polyethylene blending and modifying.Because the performance of blend descends with the increase of lower-molecular-weight component content, and the consumption of lower-molecular-weight component could obviously improve the flowability of UHMWPE when 30% left and right sides, this makes the more former UHMWPE resin of performance of blend descend very big.
United States Patent (USP) 4853427,4487857, Japanese Patent 1-272603 have reported the method with UHMWPE and compound lubricant blending and modifying.Because the modifier components complexity, large usage quantity (more than 15 parts) is difficult to make the UHMWPE steady flow and keeps its premium properties simultaneously.
Chinese patent 98100960 has been reported the method with UHMWPE and high molecule liquid crystal blending and modifying.It is to utilize the original position compounding technology, and high molecule liquid crystal and auxiliary agent are mixed with UHMWPE, by the orientation and the lubrication of high molecule liquid crystal, improves the flowability of UHMWPE.But because liquid crystal costs an arm and a leg, large usage quantity (more than 10%) makes this technology be difficult to use aborning.
Reported a kind of method that directly in polymeric kettle, prepares polyethylene/inorganic filler composite material in the Chinese patent 97120157, this method is carried out the preparation of vinyl polymerization and matrix material synchronously, products therefrom can be directly used in injection moulding, but this method relates to the change of polymerization process, and difficulty is bigger in actually operating.
Reported working method in the Chinese patent 9919536 with the extruded processing of the lubricant modified UHMWPE of naphthane, low molecular weight polyethylene wax, amides, but the used lower molecular weight properties-correcting agent of this method is too many, intensity also descends to some extent, and has limited its application.
Three, summary of the invention
The objective of the invention is provides a kind of super high molecular weight polyethylene blend that can be used for extruding and working method thereof at the prior art deficiency, adopt general macromolecule modifier and super-high molecular weight polythene blending, the shortcoming that the valency that this macromolecule modifier had both overcome liquid crystal polymer is expensive, processing temperature is high has been avoided the influence of low molecule properties-correcting agent to the physical and mechanical properties of ultrahigh molecular weight polyethylene(UHMWPE) again.This macromolecule modifier has greatly improved the processing fluidity of ultrahigh molecular weight polyethylene(UHMWPE), uses common extrusion equipment just can carry out extrusion moulding to it easily.Simultaneously, the ultrasonic vibration at extruding dies place can obviously reduce extrusion pressure and melt viscosity, improves extrusion efficiency.
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.
The recipe ingredient that can be used for extruding the super high molecular weight polyethylene blend of processing is:
The ultrahigh molecular weight polyethylene(UHMWPE) molecular weight is 100-500 ten thousand 60-90 parts
Polypropylene 40-10 part
Oxidation inhibitor 0.1-2.5 part
Nucleator 0.1-1 part
Additive 0.5-5 part
Wherein polypropylene is an isotactic polyprophlene, and melt flow index is 1-20g/min.
Oxidation inhibitor is four [β-3,5-di-tert-butyl-4-hydroxy phenyl propionic acid] pentaerythritol ester, 1,1,3-three (2-methyl-4-hydroxyl-5-t-butyl-phenyl) butane and/or three (2, the 4-di-tert-butyl-phenyl) at least a in the phosphorous acid ester, the amount that is added is generally the 0.1-2.5% of raw material blending ingredients total amount.
Nucleator is at least a in Sodium Benzoate, talcum powder, mica and/or the nano silicon.
Additive is at least a in calcium stearate, Zinic stearas and/or the polyethylene wax.Its effect is to increase flowing of polymkeric substance.
Carry out adding macromolecule modifier in the extrusion moulding process at ultrahigh molecular weight polyethylene(UHMWPE), can greatly improve the processing fluidity of ultrahigh molecular weight polyethylene(UHMWPE).And after cooling, this modifier can play the effect of toughener again, thereby obtains good processibility and physical and mechanical properties to greatest extent.In extrusion, apply ultrasonic vibration, can further reduce extrusion pressure, improve extrusion efficiency.As shown in table 1, along with polyacrylic adding, the melt flow index of system significantly increases, and illustrates that the flowability of ultrahigh molecular weight polyethylene(UHMWPE) is able to remarkable improvement.
The present invention has the following advantages: to equipment require lowly, technology is simple, the efficient height, cost is low, is easy to suitability for industrialized production, and performance and pure ultra-high molecular mass polyethylene quite or slightly improve.
Four, embodiment
Below by embodiment this patent is specifically described; be necessary to be pointed out that at this: present embodiment only is 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 cannot make some nonessential improvement and adjustment according to the content of foregoing invention.
Example 1
With 90 gram molecular weights is 1,500,000 ultra high molecular polyethylene and 10 gram isotactic polyprophlene F401 and 0.5 gram, four [β-3,5-di-tert-butyl-4-hydroxy phenyl propionic acid] pentaerythritol ester, 1 the gram polyethylene wax, 0.5 the gram Zinic stearas, 0.3 gram nano silicon (median size 10nm) mixes, and extrudes with single-screw machine again.Processing condition are detailed to be shown in Table 2, and the extrudate performance is as shown in table 3.
Example 2
With 80 gram molecular weights at 2,500,000 ultra high molecular polyethylene and 20 gram isotactic polyprophlene F401 and 0.2 gram 1,1,3-three (2-methyl-4-hydroxyl-5-t-butyl-phenyl) butane, 0.6 restrain three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, 2 gram polyethylene waxs, 1 gram calcium stearate, 0.5 gram Sodium Benzoate mix, extrude with single-screw machine again, and apply the ultrasonic vibration of 200W at mouth mould place.Processing condition are as shown in table 2, and the extrudate performance is as shown in table 3.
Example 3
With ultra high molecular polyethylene and 30 gram isotactic polyprophlene F401s and 0.8 gram 1 of 70 gram molecular weights at three and one-half million, 1,3-three (2-methyl-4-hydroxyl-5-t-butyl-phenyl) butane, 2 gram calcium stearates, 0.5 gram Sodium Benzoate mica, 0.5 gram nano silicon (median size 10nm) mix, and extrude with single-screw machine again.Processing condition are as shown in table 2, and the extrudate performance is as shown in table 3
The melt flow index of table 1 super high molecular weight polyethylene blend
PP％ 5 10 20 25MFI(230℃，12.16kg) 0.02 0.11 0.47 0.66
Table 2: the extrusion temperature example feeding section ℃ compression section ℃ homogenizing zone of super high molecular weight polyethylene blend ℃ outlet ℃ 1 140 200 230 2,102 160 220 240 2,203 190 230 250 230
Table 3: pure UHMWPE example 1 example of the mechanical property embodiment of super high molecular weight polyethylene blend extrudate 2 examples 3 Young's modulus MPa 528 700 1,030 1120 impact strength MPa 92 (P) 105 (P) 77 65 yield strength MPa 23 25 26 26 polishing scratch width mm 6.5 5.7 5.4 5.8 extrusion neck ring mold pressure MPa-4.1 2.3 3.0P: part fracture
Claims (5)
1, a kind of super high molecular weight polyethylene blend that can be used for is characterized in that the recipe ingredient (by weight) of this blend is:
Ultrahigh molecular weight polyethylene(UHMWPE), molecular weight are 100-500 ten thousand 60-90 parts
Polypropylene 40-10 part
Oxidation inhibitor 0.1-2.5 part
Nucleator 0.1-1 part
Additive 0.5-5 part
Wherein polypropylene is an isotactic polyprophlene, and melt flow index is 1-20g/min.
2, according to the described super high molecular weight polyethylene blend that can be used for of claim 1, it is characterized in that oxidation inhibitor is four [β-3,5-di-tert-butyl-4-hydroxy phenyl propionic acid] pentaerythritol ester, 1,1, at least a in 3-three (2-methyl-4-hydroxyl-5-t-butyl-phenyl) butane and/or three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester.
3,, it is characterized in that nucleator is at least a in Sodium Benzoate, talcum powder, mica and/or the nano silicon according to the described super high molecular weight polyethylene blend that can be used for of claim 1.
4,, it is characterized in that additive is a calcium stearate, at least a in Zinic stearas and/or the polyethylene wax according to the described super high molecular weight polyethylene blend that can be used for of claim 1.
5, according to the described preparation method who can be used for super high molecular weight polyethylene blend of claim 1-4, it is characterized in that:
(1) with ultra high molecular polyethylene, molecular weight is 100-500 ten thousand 60-90 parts, isotactic polyprophlene 40-10 part, and oxidation inhibitor 0.1-2.5 part, nucleator 0.1-1 part and other additive 0.5-5 part mix in super mixer,
(2) be 0-300W with said mixture at ultrasonic power, under the ultrasonic wave effect of frequency 20000-100000HZ, extrude with single screw extrusion machine, its extrusion temperature is: feeding section: 140-200 ℃, compression section: 190-260 ℃, homogenizing zone: 220-280 ℃, outlet: 200-250 ℃, extrusion moulding.
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| CNB021336741A CN1180013C (en) | 2002-08-29 | 2002-08-29 | Super high molecular weight polyethylene blend capable of using in extrusion processing and its processing method |
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| CNB021336741A CN1180013C (en) | 2002-08-29 | 2002-08-29 | Super high molecular weight polyethylene blend capable of using in extrusion processing and its processing method |
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| CN1180013C CN1180013C (en) | 2004-12-15 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371379C (en) * | 2006-03-28 | 2008-02-27 | 四川大学 | Ultrahigh molecular weight polyethylene composition capable of being extrusion molded and its prepn process |
| CN102585332A (en) * | 2012-02-27 | 2012-07-18 | 江苏科技大学 | Modified ultra-high molecular weight polyethylene material |
| CN102675715A (en) * | 2012-05-11 | 2012-09-19 | 河北北塑管业有限公司 | Ultra-high molecular weight polyethylene tube and production technique thereof |
| CN104558737A (en) * | 2013-10-10 | 2015-04-29 | 黑龙江鑫达企业集团有限公司 | Marine wear-resistant ultrahigh-molecular-weight polyethylene composite material |
| CN110684262A (en) * | 2019-10-12 | 2020-01-14 | 福建师范大学 | Preparation method of wear-resistant scratch-resistant composite material |
| CN111206296A (en) * | 2020-03-17 | 2020-05-29 | 东方交联电力电缆有限公司 | Preparation method of ultra-high molecular weight polyethylene and isotactic polypropylene blend ultra-tensile strength fiber |
| CN113554216A (en) * | 2021-06-28 | 2021-10-26 | 南京工业大学 | Multi-objective optimization method for mixed manufacturing of Kfold-LSTM mixed variation optimizing macromolecules |
-
2002
- 2002-08-29 CN CNB021336741A patent/CN1180013C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371379C (en) * | 2006-03-28 | 2008-02-27 | 四川大学 | Ultrahigh molecular weight polyethylene composition capable of being extrusion molded and its prepn process |
| CN102585332A (en) * | 2012-02-27 | 2012-07-18 | 江苏科技大学 | Modified ultra-high molecular weight polyethylene material |
| CN102675715A (en) * | 2012-05-11 | 2012-09-19 | 河北北塑管业有限公司 | Ultra-high molecular weight polyethylene tube and production technique thereof |
| CN104558737A (en) * | 2013-10-10 | 2015-04-29 | 黑龙江鑫达企业集团有限公司 | Marine wear-resistant ultrahigh-molecular-weight polyethylene composite material |
| CN110684262A (en) * | 2019-10-12 | 2020-01-14 | 福建师范大学 | Preparation method of wear-resistant scratch-resistant composite material |
| CN110684262B (en) * | 2019-10-12 | 2022-03-15 | 福建师范大学 | Preparation method of wear-resistant scratch-resistant composite material |
| CN111206296A (en) * | 2020-03-17 | 2020-05-29 | 东方交联电力电缆有限公司 | Preparation method of ultra-high molecular weight polyethylene and isotactic polypropylene blend ultra-tensile strength fiber |
| CN113554216A (en) * | 2021-06-28 | 2021-10-26 | 南京工业大学 | Multi-objective optimization method for mixed manufacturing of Kfold-LSTM mixed variation optimizing macromolecules |
| CN113554216B (en) * | 2021-06-28 | 2023-07-28 | 南京工业大学 | Kfold-LSTM hybrid variation optimizing polymer hybrid manufacturing multi-objective optimizing method |
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| CN1180013C (en) | 2004-12-15 |
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