CN1306034A - Extruding-injection class nm composite material of ultra-high-molecular polyethylene and clay - Google Patents
Extruding-injection class nm composite material of ultra-high-molecular polyethylene and clay Download PDFInfo
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- CN1306034A CN1306034A CN 01100016 CN01100016A CN1306034A CN 1306034 A CN1306034 A CN 1306034A CN 01100016 CN01100016 CN 01100016 CN 01100016 A CN01100016 A CN 01100016A CN 1306034 A CN1306034 A CN 1306034A
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Abstract
An extruding-injection class nm composition of ultrahigh-molecular polyethylene and day is prepared through in-situ graft and intercalation of clay and compounding it with ultrahigh-molecular polyethylene. Said composition can be used for extruding or injection with high efficiency.
Description
The present invention relates to a kind of ultra-high molecular weight polyethylene composite material, specially refer to the ultra-high molecular weight polyethylene composite material that to use traditional extrusion injection molding method processing.
Ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE) is a kind of engineering plastics with excellent comprehensive physical and mechanical properties, and it has common polythene and incomparable wear resistance, erosion resistance, shock-resistance and the resistance to low temperature of other engineering plastics.But because its molecular weight very high (viscosity-average molecular weight is more than 1,500,000), molecule interchain entanglement degree height makes that its melt viscosity is high, and melt flow index is zero.This causes the difficulty of processing of UHMWPE very big, can't use common extruding or injection moulding 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 limited 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, as the single screw extrusion machine of special use.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, with lubricant, 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 been 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 (closely 10 times of unmodified resin), large usage quantity (more than 10 parts) makes this technology be difficult to use aborning.
Applicant has been reported a kind of method that directly prepares the compound sharp material of polyethylene/mineral filler in polymeric kettle in Chinese patent 97120157, the preparation of this method vinyl polymerization and matrix material is carried out synchronously, products therefrom can be directly used in injection moulding, and this method can be used in the preparation molecular weight at the ultrahigh molecular weight polyethylene(UHMWPE)/inorganic filler composite material below 2,500,000.
The performance of UHMWPE goods obviously descends after the modification in order to overcome in the prior art, the UHMWPE melt flow is unstable and become the high shortcoming of written or printed documents, the invention provides a profit and has nm composite material of ultra-high-molecular polyethylene and clay of excellent properties and well processed characteristic and preparation method thereof.Nm composite material of ultra-high-molecular polyethylene and clay and preparation method thereof.
The situ-formed graft intercalation technique is grafted monomer to be inserted between two-dimentional silicate clay sheet of material carry out in-situ polymerization, obtains composite nano polymer/clay material.Wherein silicate component its lamella when excellent mechanical property is provided is orientated in flow process, played the effect that reduces the melt flow resistance, improved the processing characteristics of UHMWPE, made UHMWPE can use traditional extruding and the injection moulding process moulding, extremely wide application prospect has been arranged.
The component and the content of nm composite material of ultra-high-molecular polyethylene and clay raw material of the present invention following (weight part):
Ultrahigh molecular weight polyethylene(UHMWPE) 100
Clay 0.05-30
Intercalator 0.05-30
Dispersion medium 1-50
Additive 0.01-5
The present invention general ultrahigh molecular weight polyethylene(UHMWPE) be meant that viscosity-average molecular weight is at 1,500,000 to 5,000,000 industrial goods.
Clay provided by the present invention is that a class mineral major ingredient is the layered silicate that contains the 85-93% polynite.Its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two, and the unit cell area is 2 * 5.15 * 8.9A
2, specific surface area 700-800m
2/ g.Interlayer cation Na
+, Ca
2+, Mg
22+Deng being the interchangeability positively charged ion, after the organic ammonium salt exchange, can make between the macromolecular chain interposed layer.Clay mineral has cationic exchange total volume (CEC) 50-200meq/100g.
The clay particle diameter is generally 40-70 m, and lamellar spacing is 9.6A, and interfloor distance is 2-5A, and the interfloor distance of intercalation soil is increased to 15-20A, and the clay layer spacing is increased to 30-50A behind the situ-formed graft intercalation.
Clay content is 0.05-30 part in the present invention, and when content is lower than 0.05 part, sticking scholar is not enough to reduce the viscosity of UHMWPE melt, and when content surpasses 30 parts, clay is reunited in polymeric matrix and caused performance of composites obviously to descend.In the present invention, the clay optimum content is 0.5-10 part.
Intercalator of the present invention is the monomer that non-ionic type intercalator dibutyl maleate, methylene-succinic acid, vinylbenzene etc. contain unsaturated link(age).
Dispersion agent of the present invention can be acetone, ethanol, whiteruss etc.
The additive that the present invention adopts is initiator, oxidation inhibitor.Initiator can be BPO, DCP, DHBP; Oxidation inhibitor can be antioxidant 264, antioxidant CA, antioxidant 1010 etc.Additive can separately or be used.
Ultrahigh molecular weight polyethylene(UHMWPE) of the present invention is to be undertaken by following step:
(1) is that clay 0.05-30 part of 50-200meq/100g is mixed with 0.05-30 part intercalator with the cationic exchange total volume, and under 60-120 ℃, carries out intercalation processing.
(2) the sticking scholar after the intercalation processing and 0.01-5 part additive are scattered in 1-50 part dispersion medium.
(3) above-mentioned mixed solution and 100 portions of ultrahigh molecular weight polyethylene(UHMWPE)s were stirred 5-10 minute in high speed kneader high speed, mix the back and under 80-130 ℃, carry out the situ-formed graft intercalation.
(4) above-mentioned product is extruded with twin screw extruder at 190-260 ℃, can discharging standby.The processing temperature of extruded product such as tubing, sheet material, profiled material is 210-260 ℃.
This matrix material can be in 210 ℃-250 ℃ of injection temperatures, injection molding under the processing conditions of injection pressure 60-120Mpa.Twin screw rotating speed, screw configuration are identical with other plastic working.
Situ-formed graft intercalation technique provided by the invention is at first intercalator to be inserted between accurate two-dimentional silicate clay sheet layer material, and then rely on intercalation monomer clay layer to be strutted at the heat of polymerization of interlayer, simultaneously monomer-grafted in the ultrahigh molecular weight polyethylene powder surface, rely on the bridge linking effect of grafted monomer, clay is scattered in its melt in the melting process of ultrahigh molecular weight polyethylene(UHMWPE).Because the orientation of clay in polyethylene melt of nanoscale played the effect that reduces melt viscosity, makes ultrahigh molecular weight polyethylene(UHMWPE) can use traditional extruding with the injection moulding mode and processes.Compare with alternate manner, strong to the adaptability of equipment, technology is simple, the efficient height, and cost is low, is easy to industrial applications, and performance and bulk material quite or slightly improve.
Embodiment 1:
With the cationic exchange total volume is that the sticking scholar 20g of 100meq/100g and intercalator dibutyl maleate or vinylbenzene 10g mix the back 60 ℃ of insulations 1 hour down, then mixture and initiator B PO are joined in the 50g ethanol, again dispersion liquid and 1000g ultrahigh molecular weight polyethylene(UHMWPE) were stirred 5 minutes in high speed kneader high speed, products therefrom is extruded on forcing machine after the insulation discharging in 1 hour down in 100 ℃, and each section of forcing machine temperature is: 200 ℃, 230 ℃, 230 ℃, 225 ℃.Injection molding on injector behind the granulating and drying, its each section of injector temperature is: 1 section 190 ℃, 2 sections 230 ℃, 3 sections 230 ℃, nozzle is 220 ℃, and injection pressure is 80MPa.Measure the d of material medium clay soil through the X-ray diffraction
001The spacing of face diffraction peak and transmission electron microscope observation clay layer thickness show that clay is strutted, and spacing is 2-5nm, and clay is dispersed in the ultrahigh molecular weight polyethylene(UHMWPE) matrix with nanoscale, and mechanical property sees Table 1.
Table 1
* test condition: 230 ℃, 5kg embodiment 2-5, with example 1, clay content is respectively 20g, 30g, 40g, 50g.Its mechanical property sees Table 1.
| Embodiment | ????1 | ????2 | ????3 | ????4 | ????5 |
| Clay content (gram) | ????10 | ????20 | ????30 | ????40 | ????50 |
| UHMWPE content (gram) | ???1000 | ????1000 | ????1000 | ????1000 | ????1000 |
| Tensile strength (MPa) | ????32 | ????34 | ????35 | ????35 | ????38 |
| Tensile modulus (GPa) | ????1.0 | ????1.2 | ????1.2 | ????1.3 | ????1.4 |
| Shock strength (J/m) | ?950 | ?910 | ?900 | ?880 | ?850 |
| Wear rate (%) | ?0.25 | ?0.23 | ?0.22 | ?0.20 | ?0.15 |
| Melt flow index (g/10min) * | ?0.16 | ?0.18 | ?0.25 | ?0.30 | ?0.34 |
Claims (7)
1. extruding-injection class super-high molecular weight polyethylene clay nanocomposites is characterized in that described nm composite material of ultra-high-molecular polyethylene and clay raw material comprises following component and content (weight part):
Ultrahigh molecular weight polyethylene(UHMWPE) 100
Clay 0.05-30
Intercalator 0.05-30
Dispersion medium 1-50
Additive 0.01-5
2. according to the described a kind of extruding-injection class super-high molecular weight polyethylene clay nanocomposites of claim 1, it is characterized in that described raw clay is the layered silicate that contains the 85-93% polynite, particle diameter is 40-70 m, cation exchange capacity is 50-200meq/100, clay layer thickness is 9.6A, and interfloor distance is 2-5A.
3. a kind of extruding-injection class super-high molecular weight polyethylene clay nanocomposites according to claim 1 is characterized in that described ultrahigh molecular weight polyethylene(UHMWPE) matrix is that viscosity-average molecular weight is 1,500,000 to 5,000,000 polyethylene.
4. a kind of extruding-injection class super-high molecular weight polyethylene clay nanocomposites according to claim 1 is characterized in that described intercalator is methylene-succinic acid, dibutyl maleate, vinylbenzene.
5. a kind of extruding-injection class super-high molecular weight polyethylene clay nanocomposites according to claim 1 is characterized in that described dispersion medium is acetone, ethanol or whiteruss.
6. a kind of extruding-injection class super-high molecular weight polyethylene clay nanocomposites according to claim 1 is characterized in that described additive is initiator DCP, BPO or DHBP; Antioxidant 264, antioxidant CA or antioxidant 1010.
7. the preparation method of a kind of extruding-injection class super-high molecular weight polyethylene clay nanocomposites according to claim 1 is characterized in that being undertaken by following step:
(1) is that clay 0.05-30 part of 50-200meq/100g is mixed with 0.05-30 part intercalator with the cationic exchange total volume, and under 60-120 ℃, carries out intercalation processing.
(2) clay after the intercalation processing and 0.01-5 part additive are scattered in 1-50 part dispersion medium.
(3) above-mentioned mixed solution and 100 portions of ultrahigh molecular weight polyethylene(UHMWPE)s were stirred 5-10 minute in high speed kneader high speed, mix the back and under 80-130 ℃, carry out the situ-formed graft intercalation.
(4) above-mentioned product is extruded with twin screw extruder at 190-260 ℃, can discharging standby.
(5) injection temperature is 210 ℃-260 ℃, and injection pressure is 60-120Mpa.The processing temperature of extruded product such as tubing, sheet material, profiled material is 210-260 ℃.
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|---|---|---|---|
| CN 01100016 CN1306034A (en) | 2001-01-03 | 2001-01-03 | Extruding-injection class nm composite material of ultra-high-molecular polyethylene and clay |
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|---|---|---|---|
| CN 01100016 CN1306034A (en) | 2001-01-03 | 2001-01-03 | Extruding-injection class nm composite material of ultra-high-molecular polyethylene and clay |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100335550C (en) * | 2004-12-24 | 2007-09-05 | 上海化工研究院 | Method for preparing Nano composite material of polyethylene in super high molecular weight |
| CN1575316B (en) * | 2001-10-23 | 2010-07-21 | 亚什兰许可和知识产权有限公司 | Thermosetting inorganic clay nanodispersions and their use |
| CN105385087A (en) * | 2015-12-22 | 2016-03-09 | 合肥仲农生物科技有限公司 | High-strength nanocomposite |
| CN108137730A (en) * | 2015-09-24 | 2018-06-08 | 埃克森美孚化学专利公司 | Use the polymerization of the pyridyl group diamino compounds in the processed phyllosilicate supported on carriers of organo-aluminium |
| CN109371475A (en) * | 2018-10-12 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of spinning process of ultra-high molecular weight polyethylene |
| CN109890879A (en) * | 2016-09-06 | 2019-06-14 | 阿斯卡拉波股份有限公司 | Method for manufacturing the cross moulding body being made of UHMWPE |
-
2001
- 2001-01-03 CN CN 01100016 patent/CN1306034A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1575316B (en) * | 2001-10-23 | 2010-07-21 | 亚什兰许可和知识产权有限公司 | Thermosetting inorganic clay nanodispersions and their use |
| CN100335550C (en) * | 2004-12-24 | 2007-09-05 | 上海化工研究院 | Method for preparing Nano composite material of polyethylene in super high molecular weight |
| CN108137730A (en) * | 2015-09-24 | 2018-06-08 | 埃克森美孚化学专利公司 | Use the polymerization of the pyridyl group diamino compounds in the processed phyllosilicate supported on carriers of organo-aluminium |
| CN108137730B (en) * | 2015-09-24 | 2021-10-29 | 埃克森美孚化学专利公司 | Polymerization process using pyridyldiamido compound supported on organoaluminum-treated layered silicate support |
| CN105385087A (en) * | 2015-12-22 | 2016-03-09 | 合肥仲农生物科技有限公司 | High-strength nanocomposite |
| CN109890879A (en) * | 2016-09-06 | 2019-06-14 | 阿斯卡拉波股份有限公司 | Method for manufacturing the cross moulding body being made of UHMWPE |
| CN109371475A (en) * | 2018-10-12 | 2019-02-22 | 中国石油化工股份有限公司 | A kind of spinning process of ultra-high molecular weight polyethylene |
| CN109371475B (en) * | 2018-10-12 | 2021-04-06 | 中国石油化工股份有限公司 | Spinning method of ultra-high molecular weight polyethylene |
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