CN1438264A - Method for preparing super-high molecular-weight polyethylene self-reinforcing material and apparatus thereof - Google Patents
Method for preparing super-high molecular-weight polyethylene self-reinforcing material and apparatus thereof Download PDFInfo
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Abstract
The invention discloses a preparing method of super-high molecular-weight polythene self-strengthening material and the equipment. It mixes organic clay and super-high molecular-weight polythene to make particles to get super-high molecular-weight polythene/clay nano compound. It uses extruder to extrude the compound by melting, then make one or two-way stretch to get one or two way self-strengthening material of the compound. The intensity is improved by 5-30 times and the yield strength can reach 600 MPa.
Description
(1) described technical field
The present invention relates to the preparation method and the equipment of a kind of ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) self-reinforced material.
(2) background technology
At present, the actual strength of metallic substance has reached 80% of theoretical value, and actual modulus has reached 90% of theoretical value.And the actual strength of polymer materials has only 0.3% of theoretical value, and actual modulus has only 1% of theoretical value.The intensity of material is by microtexture decision, and therefore, increasing substantially its intensity by the microtexture that changes polymkeric substance is the focus of polymeric material field in recent years.
The polymkeric substance self-reinforced material is meant by certain method for processing forming and changes the polymer materials that intensity that the aggregated structure of polymkeric substance obtains increases substantially.Just form wild phase at polymeric acceptor in mutually, this wild phase generally is height-oriented fento or uncrimping chain crystallization, because wild phase forms rather than outer interpolation in mutually at body, so is called self-enhancement.
Adopt the crystal of the polyethylene products that traditional diamond-making technique obtains to be mainly spherocrystal, so-called spherocrystal is meant the crystal that is bent and twisted and radially form to all directions development along nucleus by the secondary platelet of initial platelet ramose in process of growth.The intensity of the PE goods of traditional method processing and modulus are decided by spherocrystal interface region structure, platelet crystal boundary area structure and non-crystalline region structure (the lax knitting wool unity structure that curls).In other words, the spherocrystal of PE goods, platelet and non-crystalline region are to combine by the Van der Waals force that hangs down bound energy, when being subjected to external force to do the time spent, be easy to take place slippage between the interface of spherocrystal, platelet and non-crystalline region, Here it is PE goods low modulus, low intensive reason.
Since adopting the high pressure solid phase method in 1962, the Ward of Britain Leeds university professor begins after HDPE extrudes self-enhancement research, successively develop diversified methods such as high pressure solid phase method, gel spinning-super times hot-drawing method, mouthful mould drawing-off method, melt extrusion method, realized the unidirectional and two-way self-enhancement of goods such as fiber, sheet material, tubing, some method and goods have been realized suitability for industrialized production.Wherein the Pennings by Dutch DSM N. V. adopted gel spinning-super times hot-drawing method to realize the production of ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) high strength fibre in 1979.Over nearly twenties years, the research of polyolefine self-reinforced material becomes a focus of polymeric material field.
PE high strength fibre technology of preparing is quite ripe, as gel spinning-super times hot-drawing method, ultrahigh molecular weight polyethylene(UHMWPE) is made macromolecular solution (gel) with perhydronaphthalene, macromolecular chain is fully separated twined, changed the aggregated structure of ultrahigh molecular weight polyethylene(UHMWPE) fully.Be extruded into precursor by orifice again, super multiplication amount stretches under certain temperature field then, obtains the UHMWPE fiber of the nearly 3Gpa of tensile strength.Therefore very long, the side chain of molecular chain seldom, terminal number ultrahigh molecular weight polyethylene(UHMWPE) seldom is considered to prepare the desirable feedstock of flexible chain structural polymer self-reinforced material.
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is meant that viscosity-average molecular weight greater than 1,500,000 polyethylene, makes a kind of thermoplastic engineering plastic of excellent combination property.Single because macromolecular chain tangles in a large number, therefore, more than melting temperature, do not have viscous state, and be elastomeric state.So this material can not adopt melt extrusion, mouthful mould drawing-off or adopt the shrinking die height of big compression ratio, middle extrusion to come out to realize self-enhancement as common polyolefine (as HDPE, PP).Can only adopt gel method (selecting for use suitable solvent that UHMWPE is prepared into dilute solution is gel) to enable to flow, be spun into fiber then or be prepared into film.
But there is complex manufacturing in following these methods, the shortcoming that cost is high.
(3) summary of the invention
The object of the present invention is to provide and a kind ofly change ultrahigh molecular weight polyethylene(UHMWPE) into viscous state by elastomeric state, its strength ratio ultrahigh molecular weight polyethylene(UHMWPE) improves 5-30 simple, lower-cost preparation method of technology doubly.Provide a kind of simple in structure, easy to operate simultaneously, the specific equipment of the two-way self-reinforced material of preparation that reinforced effects is good.
The invention discloses a kind of preparation method of super-high molecular-weight polythene self-strengthening, be prepared (a) as follows and adopt graft process to organise laminated clay, make organized clay; (b) it is even organized clay to be added dispersant, make the organic clay mixture, clay mixture and ultrahigh molecular weight polyethylene(UHMWPE) in high speed mixer, are stirred, use the forcing machine extruding pelletization, make the ultra-high-molecular polyethylene and clay nano-complex; (c) with melt extrusion method above-mentioned nano-complex is processed, made self-reinforced material.
Method of the present invention, its mixture can melt extrude with forcing machine, and carries out longitudinal stretching, makes unidirectional self-reinforced material.
In order to obtain more high-intensity unidirectional self-reinforced material, ultra-high-molecular polyethylene and clay nano-complex of the present invention, with forcing machine melt extrude leave head after, enter the device of an accurate temperature controlling, these 20 ℃-140 ℃ of draft temperature scopes, enter the drawing die that inner chamber is taper then, carry out longitudinal stretching by up-coiler.
Method of the present invention, its mixture also can melt extrude with forcing machine, and the turning unit on rotating head carries out longitudinal stretching with tractor simultaneously with the material circumgyration stretch, makes two-way self-reinforced material.
The weight percent that method of the present invention, its laminated clay account for self-reinforced material is 0.5-20%.
It is layered silicate more than 85% that method of the present invention, its employed laminated clay are preferably polynite content.
The equipment that the preparation method of super-high molecular-weight polythene self-strengthening of the present invention is used, form by forcing machine, head, tractor, the outlet end of rotating head has a turning unit that along the circumferential direction rotates, and turning unit is driven by the drive unit of adjustable speed.
After the inorganic lamellar material of nanoscale (as clay) was extruded with ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) blend, very big variation had taken place in the condensed state structure of polymkeric substance (UHMWPE).Under molten state, melt changes viscous state into by elastomeric state.So, under the melt condition, adopt nano layered silicate that a large amount of random entanglement of ultrahigh molecular weight polyethylene(UHMWPE) is untied, carry out self-enhancement again and handle (as unidirectional super drawing, rotating head two-way stretch), just can obtain the super-high molecular-weight polythene self-strengthening that intensity increases substantially, this is one of the simplest, method that cost is minimum that obtains up to now the polyolefine self-reinforced material.
Adopt the method for melt extrusion, unidirectional or two-way stretch, laminated clay modified ultrahigh molecular weight polyethylene(UHMWPE) mixture to nanoscale carries out unidirectional or two-way self-enhancement, prepares and have high strength the super-high molecular-weight polythene self-strengthening of (improving 5-30 doubly than ultrahigh molecular weight polyethylene(UHMWPE) intensity).
Main points of the present invention are: after 1, certain laminated clay (polynite content is the layered silicate more than 85%) being organised, with organic clay and ultrahigh molecular weight polyethylene(UHMWPE) (molecular weight is 150--600 ten thousand) blend, extruding pelletization, laminated clay is evenly dispersed in the ultrahigh molecular weight polyethylene(UHMWPE) with nano-scale, obtains having the ultra-high-molecular polyethylene and clay nano-complex of certain flowability.
2, adopt forcing machine (single screw rod or twin screw extruder) that the ultra-high-molecular polyethylene and clay nano-complex is melt extruded, and, obtain super-high molecular-weight polythene self-strengthening with carrying out unidirectional or two-way stretch.This YIELD STRENGTH can reach more than the 100MPa, can reach 600MPa.
Now details are as follows with prescription, equipment, the production technique of super-high molecular-weight polythene self-strengthening:
The preparation of A, ultra-high-molecular polyethylene and clay nano-complex
The preparation of a, organic clay
(include but not limited to C with various intercalators
16-20Alkyl quaternary ammonium salts, organic cation monomer such as methylacryoyloxyethyl trimethyl ammonium chloride be called for short DMC, non-ionic monomer such as vinylbenzene, acrylamide etc.) with granularity be that the laminated clay such as the sodium bentonite of micron order (100 μ m are following) carries out intercalation, obtain organic clay.Concrete intercalation method will illustrate in conjunction with the embodiments.
The preparation of b, organic clay mixture
With corresponding dispersion agent (including but not limited to ethanol, acetone, polyethylene wax etc.) organic clay and corresponding a small amount of additive (initiator such as the BPO that refer to monomer polymerization) are uniformly dispersed, obtain the organic clay mixture.Concrete dispersing method will illustrate in conjunction with the embodiments.
The preparation of c, ultra-high-molecular polyethylene and clay nano-complex
(clay content 0.5--20% wt%) stirred 20 minutes in high speed mixer with organic clay mixture and ultrahigh molecular weight polyethylene(UHMWPE).With mixed ultrahigh molecular weight polyethylene(UHMWPE) twin screw extruder extruding pelletization, the granulation process top temperature is 210 ℃, extrudes φ 5mm bar, and water-cooled is by the dicing machine pelletizing.Obtain the ultrahigh molecular weight polyethylene(UHMWPE) mixture of organic clay modification.Peel off, be broken into nano-grade size at this process medium clay soil, mixture has certain fluidity, and its melt flow rate (MFR) (MFR) is about 0.05--0.5g/10min.
The preparation of B, the unidirectional self-reinforced material of ultrahigh molecular weight polyethylene(UHMWPE)
With forcing machine (single, double screw extrusion press) ultra-high-molecular polyethylene and clay nano-complex pellet is melt extruded, extrusion temperature is no more than 220 ℃.The melt of extruding enters head and forms bar, enter the device of an accurate temperature controlling then, the draft temperature scope is 20 ℃-140 ℃, enter drawing die (seeing accompanying drawing 1) then, tractor or up-coiler are pressed certain stretch ratio with the bar longitudinal stretching, make material self-enhancement on draw direction, obtain the unidirectional self-reinforced material of ultrahigh molecular weight polyethylene(UHMWPE).Preparation technology's flow process is seen accompanying drawing 2.
The preparation of C, the two-way self-reinforced material of ultra-high-molecular polyethylene and clay nano-complex
With forcing machine (single screw rod or twin screw extruder) ultra-high-molecular polyethylene and clay nano-complex pellet is melt extruded, extrusion temperature is no more than 220 ℃.The melt of extruding enters the rotating head (seeing accompanying drawing 3) of particular design, and the turning unit on the rotating head is with the material circumgyration stretch of accurate temperature controlling, and the draft temperature scope is 20 ℃-140 ℃, makes material self-enhancement in a circumferential direction.The pipe of extruding enters tractor and stretches, and makes material self-enhancement in the axial direction.Obtain the two-way self-reinforced material of ultrahigh molecular weight polyethylene(UHMWPE) at last.Preparation technology's flow process is seen accompanying drawing 4.
The concrete structure of rotating head 15 of the present invention is as shown in Figure 3: be made up of external mold 6, torpedo body 7, splitter 8, plug 9, plug temperature regulating device 10, external mold temperature regulating device 11, turning unit 12, gear 13.Turning unit 12 is positioned at the end of rotating head, is the right cylinder of hollow, and intracavity diameter equals the external diameter of rotating head discharge port place extrudate.Turning unit comes driven rotary by gear 13 by drive unit.
Therefore, preparation method of the present invention changes ultrahigh molecular weight polyethylene(UHMWPE) into viscous state by elastomeric state, and its strength ratio ultrahigh molecular weight polyethylene(UHMWPE) improves 5-30 doubly, and technology is simple, cost is lower.The specific equipment of while preparation self-reinforced material of the present invention has simple in structure, easy to operate, and reinforced effects is good.
(4) description of drawings:
Accompanying drawing 1 is the drawing die structural representation
Accompanying drawing 2 is unidirectional self-reinforcing process flow process principle sketch
Accompanying drawing 3 is the rotating head structural representation
Accompanying drawing 4 is two-way self-reinforcing process flow process principle sketch.
1 is forcing machine; 2 is head; 3 is temperature regulating device; 4 is drawing die; 5 is up-coiler; 6 is external mold; 7 is the torpedo body; 8 is splitter; 9 is plug; 10 is the plug temperature regulating device; 11 is the external mold temperature regulating device; 12 is turning unit, and 13 is gear; 14 is forcing machine; 15 is rotating head; 16 is driving gear; 17 is drive sprocket; 18 is drive shaft; 19 is tractor
(5) embodiment 1. embodiment 1
To contain the sodium bentonite of 90% polynite and the suspension that distilled water is made into 5% (wt%), high-speed stirring 20 minutes obtains bentonite suspension.Intercalator hexadecyl brometo de amonio and distilled water are made into 10% (wt%) aqueous solution.Bentonite suspension is heated to 70--80 ℃, then quaternary ammonium salt aqueous solution is added in the suspension gradually, violent stirring 10 minutes kept temperature 1 hour, naturally cooled to room temperature, with the reaction solution suction filtration, white depositions, with deionized water wash to there not being Br
-(use Ag
+Check).With the product that makes in 80 ℃ of vacuum-drying 24h, ground 200 mesh sieves after sealing preserve.Products therefrom is organo montmorillonite.
With mixed, the grinding of organo montmorillonite and polyethylene wax, obtain the organic clay mixture by 1: 1 (weight ratio).Be that 3,000,000 ultrahigh molecular weight polyethylene(UHMWPE) mixed in high speed mixer 20 minutes again with 10 parts of organic clay mixtures and 100 parts of (parts by weight) molecular weight.Extruding pelletization on twin screw extruder then, each section of forcing machine temperature is: 120 ℃, 180 ℃, 200 ℃, 210 ℃, obtain the ultra-high-molecular polyethylene and clay nano-complex.
The ultra-high-molecular polyethylene and clay nano-complex is melt extruded on single screw extrusion machine, carry out two-way self-enhancement with rotating head, a mouthful die clearance is 2mm.Each section of forcing machine temperature is 180 ℃, and 190 ℃, 200 ℃, it is 210 ℃, 190 ℃, 170 ℃, 120 ℃ that rotating head is respectively distinguished temperature.The longitudinal stretching temperature is 120 ℃, by the true temperature control of circulating heat conduction olein.Finally obtaining vertical yield strength is 240Mpa, circumferentially yield strength is the two-way self-reinforced material of ultrahigh molecular weight polyethylene(UHMWPE) of 170Mpa.
Its used equipment is as shown in Figure 4: its used forcing machine 14 is a single screw extrusion machine, and forcing machine 14 has rotating head 15, and the drive unit that turning unit is made up of driving gear 16, drive sprocket 17, drive shaft 18, tractor 19 on the rotating head drives.
The concrete structure of rotating head 15 is as shown in Figure 3: be made up of external mold 6, torpedo body 7, splitter 8, plug 9, plug temperature regulating device 10, external mold temperature regulating device 11, turning unit 12, gear 13.Turning unit 12 is positioned at the end of rotating head, is the right cylinder of hollow, and intracavity diameter equals the external diameter of rotating head discharge port place extrudate.Turning unit comes driven rotary by gear 13 by drive unit.2. embodiment 2
To contain the sodium bentonite of 95% polynite and the suspension that distilled water is made into 5% (wt%), high-speed stirring 20 minutes obtains bentonite suspension.DMC and distilled water are made into 10% (wt%) aqueous solution.2 times of DMC aqueous solution to polynite exchangable ion capacity are mixed with bentonite suspension, and under 60 ℃, violent stirring 2h naturally cools to room temperature, with the reaction solution suction filtration, white depositions, with deionized water wash to there not being Cl
-(use Ag
+Check).With the product that makes in 80 ℃ of vacuum-drying 24h, ground 200 mesh sieves after sealing preserve.Products therefrom is organic clay.
The 30g organobentonite is joined in the 60g ethanol with a small amount of initiator B PO, stir 10min, obtain the organic clay mixture.Mixture is joined in the 1000g ultrahigh molecular weight polyethylene(UHMWPE), in high speed mixer, behind the mixing 10min, again blend is used the twin screw extruder extruding pelletization, promptly get the ultra-high-molecular polyethylene and clay nano-complex.
The ultra-high-molecular polyethylene and clay nano-complex is melt extruded on single screw extrusion machine, the melt of extruding enters head and forms bar, enter an accurate temperature controlling device then, after accurate temperature controlling makes the temperature of bar be controlled at 120 ℃, enter drawing die, up-coiler is pressed certain stretch ratio with the bar longitudinal stretching.Each section of forcing machine temperature is 180 ℃, and 190 ℃, 200 ℃, head temperature is 190 ℃.Finally obtaining vertical yield strength is the unidirectional self-reinforced material of 440Mpa ultrahigh molecular weight polyethylene(UHMWPE).
Its used equipment is as shown in Figure 2: forcing machine 1 is a single screw extrusion machine, and forcing machine has head 2.The head back is followed successively by temperature regulating device 3, drawing die 4, up-coiler 5.After extruded material was extruded by the head of forcing machine, the temperature regulating device 3 by by the true temperature control of circulating heat conduction olein entered drawing die 4, is stretched by up-coiler 5 then.The structure of drawing die 4 is as shown in Figure 1: drawing die opening for feed inner chamber is conical, and the discharge port inner chamber is cylindrical, and inlet diameter is greater than exit diameter, and an actor's rendering of an operatic tune is the stepped hole of 45 ° of convergent angle.3. embodiment 3
To contain the sodium bentonite of 85% polynite and the suspension that ethanol is made into 30% (wt%), high-speed stirring 20 minutes obtains montmorillonite suspension liquid.2 times of vinylbenzene to polynite exchangable ion capacity under 60 ℃, behind the violent stirring 1h, are cooled to room temperature, add a spot of initiator B PO, continue to stir 30min.Products therefrom is the organic clay mixture.
The ultra-high-molecular polyethylene and clay nano-complex is melt extruded on twin screw extruder, carry out two-way self-enhancement with rotating head, a mouthful die clearance is 2mm.Each section of forcing machine temperature is 180 ℃, and 190 ℃, 200 ℃, it is 210 ℃, 190 ℃, 170 ℃, 120 ℃ that rotating head is respectively distinguished temperature.The longitudinal stretching temperature is 120 ℃, by the true temperature control of circulating heat conduction olein.Finally obtaining vertical yield strength is 400Mpa, circumferentially yield strength is the two-way self-reinforced material of ultrahigh molecular weight polyethylene(UHMWPE) of 300Mpa.4. embodiment 4, and with embodiment 2, the accurate respectively controlled temperature of temperature regulating device is 20 ℃, 60 ℃, 80 ℃ and 100 ℃, 140 ℃.Vertical yield strength of the unidirectional self-reinforced material of gained ultrahigh molecular weight polyethylene(UHMWPE) is respectively 550Mpa, 520Mpa, 460Mpa, 450Mpa and 440Mpa.5. embodiment 5, and with embodiment 3, the accurate respectively control stretching temperature of rotating head thermal oil is 20 ℃, 90 ℃, 100 ℃ and 140 ℃.Vertical yield strength of the two-way self-reinforced material of gained ultrahigh molecular weight polyethylene(UHMWPE) is respectively 500Mpa, 450Mpa, 430Mpa, 410Mpa; Circumferentially yield strength is respectively 380Mpa, 360Mpa, 340Mpa, 310Mpa.
Claims (7)
1. the preparation method of a super-high molecular-weight polythene self-strengthening is characterized in that: be prepared (a) as follows and adopt graft process to organise laminated clay, make organized clay; (b) it is even organized clay to be added dispersant, make the organic clay mixture, clay mixture and ultrahigh molecular weight polyethylene(UHMWPE) in high speed mixer, are stirred, use the forcing machine extruding pelletization, make the ultra-high-molecular polyethylene and clay nano-complex; (c) with melt extrusion method above-mentioned nano-complex is processed, made self-reinforced material.
2. the preparation method of super-high molecular-weight polythene self-strengthening according to claim 1, it is characterized in that: described ultra-high-molecular polyethylene and clay nano-complex, melt extrude with forcing machine, and carry out longitudinal stretching, make unidirectional self-reinforced material.
3. the preparation method of super-high molecular-weight polythene self-strengthening according to claim 2, it is characterized in that: described ultra-high-molecular polyethylene and clay nano-complex, with forcing machine melt extrude leave head after, enter the device of an accurate temperature controlling, the draft temperature scope is 20 ℃-140 ℃, enter the drawing die that inner chamber is taper then, carry out longitudinal stretching by up-coiler.
4. the preparation method of super-high molecular-weight polythene self-strengthening according to claim 1, it is characterized in that: described ultra-high-molecular polyethylene and clay nano-complex, melt extrude with forcing machine, turning unit on rotating head is with the material circumgyration stretch, carry out longitudinal stretching with tractor simultaneously, make two-way self-reinforced material.
5. according to the preparation method of claim 1,2,3 or 4 described super-high molecular-weight polythene self-strengthening, it is characterized in that: the weight percent that laminated clay accounts for self-reinforced material is 0.5-20%.
6. according to the preparation method of claim 1,2,3 or 4 described super-high molecular-weight polythene self-strengthening, it is characterized in that: described laminated clay is a layered silicate more than 85% for polynite content.
7. the used equipment of preparation method of claim 1 or 3 described super-high molecular-weight polythene self-strengthening, form by forcing machine (9), head (10), tractor, it is characterized in that: the outlet end of rotating head has a turning unit (7) that along the circumferential direction rotates, and turning unit is driven by the drive unit of adjustable speed.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293980B (en) * | 2007-05-30 | 2010-09-29 | 北京中科普惠科技发展有限公司 | Thermoplastic polyalcohol/clay soil nano-composite material, preparation method and application thereof |
| CN102504382A (en) * | 2011-10-13 | 2012-06-20 | 扬州巨业耐磨复合材料有限责任公司 | Production process of nanometer modified superhigh-molecular-weight polyethylene wear-resisting pipe |
| CN104512025A (en) * | 2013-09-27 | 2015-04-15 | 青岛蓝农谷农产品研究开发有限公司 | Extrusion moulding method of wear-resistant hollow pipe |
| CN105385087A (en) * | 2015-12-22 | 2016-03-09 | 合肥仲农生物科技有限公司 | High-strength nanocomposite |
| CN112281234A (en) * | 2020-10-23 | 2021-01-29 | 江苏锵尼玛新材料股份有限公司 | Antibacterial and antiviral UHMWPE functional fiber and preparation method thereof |
| CN112895269A (en) * | 2021-02-04 | 2021-06-04 | 华南理工大学 | Polymer circulating dynamic force field pressure forming method |
| CN115012236A (en) * | 2022-07-07 | 2022-09-06 | 太原理工大学 | Low-creep low-wear mesh wire and preparation method and application thereof |
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2003
- 2003-03-04 CN CN 03111934 patent/CN1253501C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293980B (en) * | 2007-05-30 | 2010-09-29 | 北京中科普惠科技发展有限公司 | Thermoplastic polyalcohol/clay soil nano-composite material, preparation method and application thereof |
| CN102504382A (en) * | 2011-10-13 | 2012-06-20 | 扬州巨业耐磨复合材料有限责任公司 | Production process of nanometer modified superhigh-molecular-weight polyethylene wear-resisting pipe |
| CN104512025A (en) * | 2013-09-27 | 2015-04-15 | 青岛蓝农谷农产品研究开发有限公司 | Extrusion moulding method of wear-resistant hollow pipe |
| CN104512025B (en) * | 2013-09-27 | 2017-02-01 | 青岛蓝农谷农产品研究开发有限公司 | Extrusion moulding method of wear-resistant hollow pipe |
| CN105385087A (en) * | 2015-12-22 | 2016-03-09 | 合肥仲农生物科技有限公司 | High-strength nanocomposite |
| CN112281234A (en) * | 2020-10-23 | 2021-01-29 | 江苏锵尼玛新材料股份有限公司 | Antibacterial and antiviral UHMWPE functional fiber and preparation method thereof |
| CN112895269A (en) * | 2021-02-04 | 2021-06-04 | 华南理工大学 | Polymer circulating dynamic force field pressure forming method |
| CN115012236A (en) * | 2022-07-07 | 2022-09-06 | 太原理工大学 | Low-creep low-wear mesh wire and preparation method and application thereof |
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Assignee: Shandong Dongfang Pipe Industry Co., Ltd. Assignor: Wang Qingzhao Contract fulfillment period: 2008.1.1 to 2013.12.31 contract change Contract record no.: 2009370000495 Denomination of invention: Method for preparing super-high molecular-weight polyethylene self-reinforcing material and apparatus thereof Granted publication date: 20060426 License type: Exclusive license Record date: 2009.11.6 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.1.1 TO 2013.12.31; CHANGE OF CONTRACT Name of requester: SHANDONG EAST PIPELINE CO., LTD. Effective date: 20091106 |