CN1091758A - Ultra-high molecular weight polyvinyl composite and preparation method - Google Patents
Ultra-high molecular weight polyvinyl composite and preparation method Download PDFInfo
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- CN1091758A CN1091758A CN 93115101 CN93115101A CN1091758A CN 1091758 A CN1091758 A CN 1091758A CN 93115101 CN93115101 CN 93115101 CN 93115101 A CN93115101 A CN 93115101A CN 1091758 A CN1091758 A CN 1091758A
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Abstract
The invention discloses molecular weight more than 3,000,000, especially between 350～5,000,000, the mold pressing with higher heat distortion temperature and low-thermal-expansion is with ultra-high molecular weight polyvinyl composite and preparation method.Said composition is mainly added 5～25% inorganic fibre in UHMW-PE, the interpolation of inorganic fibre be the UHMW-PE that will be mixed with 0.1～1.0% fluidity improver with through the inorganic fibre of coupling agent dip treating mixing near extruding under the molten state.
Description
The present invention relates to a kind of ultra-high molecular weight polyvinyl composite, particularly have higher heat distortion temperature and the very polyethylene composition and the preparation method of macromolecule.
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMW-PE) has good wear resistance, shock resistance, chemical resistance and tensile strength because of it, uses extensive day by day as engineering plastics.But because of it does not overcome some original inherent defects of polyethylene fully, low as heat-drawn wire, creep resistance is poor, thermal expansivity is big, the feasible range of application that has limited ultrahigh molecular weight polyethylene(UHMWPE) to a certain extent.
Handle though have document to be disclosed in the ultrahigh molecular weight polyethylene(UHMWPE) to add inorganics that it is done some modification, to change and/or to improve its some performance.But ultrahigh molecular weight polyethylene(UHMWPE) as the modification object, or molecular weight is relatively little (as molecular weight about 1,000,000, this patent such as nothing particularly point out, molecular weight refers to that all viscosimetry measures) ultrahigh molecular weight polyethylene(UHMWPE), or being mixed with relatively large low or High molecular weight polyethylene reduces ultrahigh molecular weight polyethylene(UHMWPE) viscosity, increases mobile.Because molecular weight is relatively little or make viscosity reduction and handle, therefore the inorganic modified additive that adds soaks into the ultrahigh molecular weight polyethylene(UHMWPE) parent easily and is fully all mixed, thereby can reach the modification purpose.
Specially permit openly as Japanese Patent that 62-48747 is disclosed to be added inorganic filler to ultrahigh molecular weight polyethylene(UHMWPE) and change or improve some performance, ultrahigh molecular weight polyethylene(UHMWPE) as the modification object, be that molecular weight is suitable for extrusion molding about 1,000,000, and, need to add fatty acid ester and fatty acid zinc salt lubricant for making it that good processing properties be arranged.
United States Patent (USP) 4792588,5019627, and the Chinese patent 87108361.2 disclosed inorganicss that in ultrahigh molecular weight polyethylene(UHMWPE), add, related modification object then is the injection molding ultrahigh molecular weight polyethylene(UHMWPE), and it is to make a kind of composition by more a spot of ultrahigh molecular weight polyethylene(UHMWPE) (molecular weight is about 1,650,000) and relatively large low or High molecular weight polyethylene (molecular weight is 1500～360,000) through multistage polyreaction.Low or the High molecular weight polyethylene purpose of blending described in disclosed specification sheets, is intended to improve the ultrahigh molecular weight polyethylene(UHMWPE) flowability, can improve the ultrahigh molecular weight polyethylene(UHMWPE) melt-forming so on the one hand, makes it to be suitable for injection molding; Also add other modified materialses on the other hand easily and do the modification processing.
Above-mentionedly ultrahigh molecular weight polyethylene(UHMWPE) is added inorganic filler do modification and handle, related modification object all is injection or extruding ultrahigh molecular weight polyethylene(UHMWPE)s that low relatively small molecular weight of viscosity or blending have low or High molecular weight polyethylene.They all do not relate to directly and/or to more macromolecule such as molecular weight are greater than more than 3,000,000, the worse big viscosity mold pressing of flowability is added inorganic filler with ultrahigh molecular weight polyethylene(UHMWPE) and done the modification processing, does not more relate to the modification processing of making to improve heat-drawn wire.Add lubricant or blending is low or High molecular weight polyethylene, always will damage some characteristics, the especially wear resistance of ultrahigh molecular weight polyethylene(UHMWPE).This in addition method and technology conditional request height, preparation is complicated, loaded down with trivial details.
Those of ordinary skill knows that all ultrahigh molecular weight polyethylene(UHMWPE) is along with the increase of molecular weight, and its every physicochemical property will significantly improve, and show excellent comprehensive performances.But the increase of molecular weight makes ultrahigh molecular weight polyethylene(UHMWPE) viscosity become high, and mobile very poor, molecular surface tension force significantly improves, and is very difficult affine with other additive, so that causes filling-modified very difficult.It is generally acknowledged that can not (at least can not directly) it being added inorganic material carries out modification, especially improve its heat-drawn wire, because because big molecular weight brings high viscosity and the flowability of difference and big molecular surface tension force, make that the inorganics that adds is difficult to all mix with ultrahigh molecular weight polyethylene(UHMWPE) is affine.The ultrahigh molecular weight polyethylene(UHMWPE) of modification or molecular weight are less relatively from above-mentioned prior art, or need at first to reduce viscosity and increase mobilely by reducing molecular-weight average with relatively large low or High molecular weight polyethylene polymerization, can well be proved.
The object of the present invention is to provide a kind of high comprehensive performance, molecular weight is greatly about more than 3,000,000, and has the mold pressing ultra-high molecular weight polyvinyl composite of higher heat distortion temperature and low-thermal-expansion.
Another purpose of the present invention will overcome above-mentioned technology prejudice exactly, provide a kind of and easy do not damaging the ultrahigh molecular weight polyethylene(UHMWPE) performance, especially under high viscosity state directly interpolation can improve the method for the inorganics of heat-drawn wire.
The present invention's first purpose realizes, main by molecular weight greatly in the ultrahigh molecular weight polyethylene(UHMWPE) more than 3,000,000 reach admixture (adding) 5～25%(in polyethylene weight) inorganic fibre.The admixture of inorganic fibre has formed a kind of crosslinked in length and breadth skeleton in UHMW-PE, significantly improved the intensity of UHMW-PE, thereby has improved its heat-drawn wire, has also improved the expansion shrinkage.
The admixture of inorganic fibre, it is characterized in that will being mixed with (adding) 0.1～1.0%(in polyethylene weight) ultrahigh molecular weight polyethylene(UHMWPE) of fluidity improver and be heated to softening (near fusion) state and close with it temperature respectively through the inorganic fibre of coupling agent treatment, carry out mixing to fully all mixing then at mixing roll.
Ultrahigh molecular weight polyethylene(UHMWPE) of the present invention can be commodity molecular weight greatly about 3,000,000 and more than, equal, the multipolymer of especially 350～5,000,000 Alathon or ethylene copolymer, or ethene and other alpha-olefins.
The inorganic fibre volume can be 5～25%(in polyethylene weight in the ultra-high molecular weight polyvinyl composite of the present invention, does not below have to particularly point out, and volume is all in polyethylene weight), preferred volume is 10～15%.Inorganic fibre can be inorganic materials fibers such as glass fibre, carbon fiber, boron fibre.As be cut to tiny staple fibre and mix, more favourablely so fully all to mix with the polyethylene parent, effect can be better.Volume that it is generally acknowledged inorganic fibre then improves the heat-drawn wire DeGrain as less than 5%,, then is difficult for fully all mixing with the polyethylene parent greater than 25% as volume.
In the ultra-high molecular weight polyvinyl composite of the present invention, but the inorganic wear-resisting powder weighting material of admixture 2～8% also, optimizing volume is 4～6%, can improve its wear resistance, inorganic wear-resisting powder weighting material can be as bronze powder, Graphite Powder 99, aluminum oxide powder etc.Equally, but also admixture of some other powdery additive, as pigment, dyestuff, fire-retardant, insulant, weathering resistance stablizer etc., these are not that the present invention relates generally to.
For the inorganic fibre that makes admixture has wetting property preferably, improve its adhesivity to ultrahigh molecular weight polyethylene(UHMWPE), make inorganic fibre homodisperse and UHMW-PE fine affine.Inorganic fibre of the present invention should be used coupling agent treatment earlier before admixture, promptly standby with coupling agent dipping inorganic fibre and airing.Coupling agent commonly used just like, vinyltriethoxysilane (trade mark A151), γ-metacryloxy propyl trimethoxy silicane (trade mark A174), β-(3,4 epoxycyclohexyl) ethyl trimethoxy silane (trade mark A186) etc.
For the inorganic fibre that makes admixture can fully all mix with UHMW-PE, should suitably increase the flowability of improving UHMW-PE.The method that the present invention improves the UHMW-PE flowability is suitable admixture and all mixes a spot of as 0.1～1.0% solids flowability improving agent that the optimum mix amount is between 0.3～0.6%.Fluidity improver addition less than 0.1% does not then reach the effect that improves liquidity, and addition surpasses 1.0%, then easily causes the UHMW-PE mechanical property to descend.Fluidity improver can be selected for use as stearate Magnesium Stearate for example, polyethylene wax, MS
2(Beijing Chemical Engineering College's product) etc., the wherein mobile effect of improving is especially with MS
2For excellent.
Inorganic fibre and UHMW-PE all mix, and can adopt as single shaft or multishaft extruder mixing.The UHMW-PE thermoplastic that promptly will all be mixed with fluidity improver respectively is extremely near molten state; Inorganic fibre after coupling agent treatment also is heated to roughly close temperature, mixing in mixing roll then, make its full and uniform mixing promptly get ultra-high molecular weight polyvinyl composite of the present invention.Mixing especially is excellent between 130～170 ℃, this moment ultrahigh molecular weight polyethylene(UHMWPE) in the pasty state, easily by mixing, make that fiber and UHMW-PE are even to be combined.
The inorganic powder admixture can add simultaneously or after a while with fluidity improver, and stirs with UHMW-PE.
Below will be by the explanation of indefiniteness embodiment, further explain the object of the invention, scheme and advantage.
Embodiment:
Embodiment compatibility and feature performance benefit
UHMW glass graphite MS
2The heat-drawn wire wear rate % thermal expansivity strong intensity of breaking
-PE fiber powder (4.6kg/cm
2) (husky mill test) 10
-4/ ℃ N/cm
2
Contrast 100 000 80 ℃ 0.74 1.5 2900
1 100 10 2 0.1 95℃ 0.78 1.2 3200
2 100 15 4 0.5 100℃ 0.65 1.15 3600
3 100 25 8 0.8 100℃ 1 1.05 3500
UHMW-PE is the commercial goods in the embodiment of the invention, and molecular weight is about about 400～4,500,000 (Shanghai Chemical Research Inst's product) greatly, the MS that fluidity improver selects for use the Beijing Chemical Engineering College to produce
2, inorganic fibre is selected alkali free glass fibre for use, and coupling agent adopts A151, and inorganic wear-resisting fleur adopts Graphite Powder 99.But design of the present invention and protection domain are not subjected to the foregoing description to add kind to be limited, and some those of ordinary skill think that the substituent that is equal to all at the row of this patent protection domain, do not list one by one at this.
Above-mentioned ultrahigh molecular weight polyethylene(UHMWPE), Graphite Powder 99, fluidity improver are mixed in proportion and stir, put into about 50 minutes of 160 ℃ of baking oven bakings, make it softening in the pasty state.
The non-alkali glass staple fibre of cleaning is put into commercially available coupling agent A151 solution impregnation for some time, pick up to dry to be placed in 160 ℃ of baking ovens and dried by the fire about 35 minutes.
Divide two-way to push mixingly in glass fibre after the heating and ultrahigh molecular weight polyethylene(UHMWPE) powder, glass fibre is evenly mixed in the ultrahigh molecular weight polyethylene(UHMWPE) through two roll press.It is standby that mixture after mixing can cut into required specification particle immediately.
The inventive method not only can be used for very high viscosity UHMW-PE blending inorganic fibre, and more can be used for the direct blending inorganic fibre of the low relatively UHMW-PE of viscosity.
The present invention since ultra-high molecular weight especially molecular weight greater than the molded polyethylene 3,000,000 or more in direct admixture inorganic fibre toughener, make under the performance that does not influence ultrahigh molecular weight polyethylene(UHMWPE), can significantly improve heat-drawn wire and breaking tenacity, dwindle its coefficient of expansion, thereby enlarged the UHMW-PE range of application, made it to have the use of certain temperature range occasion.The direct admixture inorganic fibre of the present invention method has not only overcome the directly technology prejudice of admixture inorganic fibre of big viscosity ultrahigh molecular weight polyethylene(UHMWPE), and doing to improve the heat-drawn wire modification simultaneously, does not damage the ultrahigh molecular weight polyethylene(UHMWPE) performance again.
Claims (10)
1, a kind of ultra-high molecular weight polyvinyl composite, include ultrahigh molecular weight polyethylene(UHMWPE) and inorganic additive, the molecular weight (viscosimetry mensuration) that it is characterized in that described ultrahigh molecular weight polyethylene(UHMWPE) is more than 3,000,000, described inorganic additive is an inorganic fibre, its volume (adds, in ultrahigh molecular weight polyethylene(UHMWPE), as follows) be 5～25%.
2,, it is characterized in that also being added with in the described composition 2～8% inorganic wear-resisting powder according to the described ultra-high molecular weight polyvinyl composite of claim 1.
3, according to claim 1 or 2 described ultra-high molecular weight polyvinyl composites, the molecular weight that it is characterized in that ultrahigh molecular weight polyethylene(UHMWPE) is 300～5,000,000.
4,, it is characterized in that described inorganic fibre is a staple fibre according to the described ultra-high molecular weight polyvinyl composite of claim 3.
5, according to the described ultra-high molecular weight polyvinyl composite of claim 4, the volume that it is characterized in that described inorganic fibre is 10～15%.
6,, it is characterized in that described inorganic wear-resisting powder volume is 4～6% according to the described ultra-high molecular weight polyvinyl composite of claim 5.
7, a kind of in ultrahigh molecular weight polyethylene(UHMWPE) the direct method of admixture modified inorganic fiber, it is characterized in that comprising that the fluidity improver with ultrahigh molecular weight polyethylene(UHMWPE) and 0.1～1.0% is evenly mixed, and be heated to softening near molten state, with inorganic fibre coupling agent dip treating, the airing post-heating is to close temperature with polyethylene, and polyethylene after will heating then and inorganic fibre are mixing to fully all mixing combination in mixing roll.
8,, it is characterized in that described Heating temperature is 130～170 ℃ according to the described method of modifying of claim 7.
9, described according to Claim 8 method of modifying is characterized in that described fluidity improver is MS
2
10,, it is characterized in that described coupling agent is A151 according to the described method of modifying of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93115101 CN1039237C (en) | 1993-11-20 | 1993-11-20 | Super-high molecular weight polyethylene compsn. and its prepn. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93115101 CN1039237C (en) | 1993-11-20 | 1993-11-20 | Super-high molecular weight polyethylene compsn. and its prepn. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1091758A true CN1091758A (en) | 1994-09-07 |
| CN1039237C CN1039237C (en) | 1998-07-22 |
Family
ID=4990792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93115101 Expired - Fee Related CN1039237C (en) | 1993-11-20 | 1993-11-20 | Super-high molecular weight polyethylene compsn. and its prepn. |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1039237C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550994B (en) * | 2009-04-14 | 2010-12-08 | 无锡永凯达齿轮有限公司 | Friction piece used for automotive belt tightener and production method thereof |
-
1993
- 1993-11-20 CN CN 93115101 patent/CN1039237C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550994B (en) * | 2009-04-14 | 2010-12-08 | 无锡永凯达齿轮有限公司 | Friction piece used for automotive belt tightener and production method thereof |
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| Publication number | Publication date |
|---|---|
| CN1039237C (en) | 1998-07-22 |
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