CN102206390B - Modification method for reinforcing polytetrafluoroethylene material through ekonol and aramid fiber - Google Patents
Modification method for reinforcing polytetrafluoroethylene material through ekonol and aramid fiber Download PDFInfo
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- CN102206390B CN102206390B CN 201110024820 CN201110024820A CN102206390B CN 102206390 B CN102206390 B CN 102206390B CN 201110024820 CN201110024820 CN 201110024820 CN 201110024820 A CN201110024820 A CN 201110024820A CN 102206390 B CN102206390 B CN 102206390B
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Abstract
The invention relates to a modification method for a polytetrafluoroethylene (PTFE) material. In order to overcome and change disadvantages of the PTFE, and improve a comprehensive property of the PTFE, the modification method for the PTFE material through ekonol and aramid fiber is provided by the present invention. The materials adopted by the method comprise, by mass, 8-28% of ekonol, 1-11% of graphite, 1-11% of aramid fiber, and the balance of the PTFE. With the present invention, the modified PTFE material with low wear rate and excellent comprehensive mechanical property can be prepared based on excellent performances of the ekonol, the aramid fiber and the graphite.
Description
Technical field
The present invention relates to polymer composite, relate in particular to a kind of method of modifying of polytetrafluoroethylmaterial material.
Background technology
Polytetrafluoroethylene (PTFE) is the high crystallinity polymer of tetrafluoroethylene monomer, it is the thermoplastics that a kind of white has the sense of wax shape, it has been formed with structures shape it and has had advantages such as high temperature resistant, that chemical property good, frictional coefficient is low, dielectricity is good, and these advantages make it be widely used in anti-attrition lining, various seal washer, valve seat etc.But compare with other plastics, its mechanical property is not fine; Linear expansivity is bigger; Molding shrinkage is big, the secondary processing difficulty; Hardness is low, and wearability is poor; Creep resistant is poor, easy-cold flow.For the shortcoming that overcomes and change PTFE, improve its over-all properties, people are devoted to the study on the modification of PTFE always.
At present, the method for modifying of tetrafluoroethylene mainly contains: surface modification, filling-modified, blending and modifying etc., wherein, filling-modified is a kind of simple effective method, both can keep its advantage, can utilize complex effect again, improves and overcome the defective of pure PTFE.Filler commonly used has: mineral filler, metal and metal oxide, nanoparticle and organic filler etc.At different situations, can add a kind of filler, also can add several fillers simultaneously, at present, widespread use is glass fibre in the filler.
The Chinese disclosure of the Invention of application number CN 201010174557.9 a kind of polytetrafluoroethylalloy alloy and preparation method thereof, this invention relates to a kind of high polymer alloy, its composition consists predominantly of the tetrafluoroethylene of 60-97wt%, the main chain polyester type liquid crystal polymer of 3-40wt%, its surplus is subsidiary material, subsidiary material include wherein one or both of carbon fiber and glass fibre, the content of carbon fiber is 0-15wt%, the content of glass fibre is 0-15wt%, and subsidiary material include the graphite of 0-5wt%.Though inventing wear-resisting polytetrafluoroethylalloy alloy, this has the wear resistance height, hardness height, advantage such as creep properties is low.But because the consistency between glass fibre and the PTFE matrix is relatively poor, avidity is less, tangible interface in matrix, occurs, and be not easy to be uniformly dispersed, so this class friction coefficient of composite material is bigger.
Summary of the invention
At present in order to overcome and change the shortcoming of tetrafluoroethylene, improve its over-all properties, carry out filling-modified to polytetrafluoroethylmaterial material, widespread use is glass fibre in the filler, but because the consistency between glass fibre and the PTFE matrix is relatively poor, avidity is less, tangible interface appears in matrix, and be not easy to be uniformly dispersed, so this class friction coefficient of composite material is bigger, therefore the present invention proposes polybenzoate and aramid fiber reinforced TFE material modification method, based on polybenzoate, the excellent properties of aramid fiber and graphite can obtain the modified materials of polytetrafluoroethyland of low wear rate and comprehensive mechanical property excellence.
The present invention is achieved by the following technical solutions: polybenzoate and aramid fiber reinforced TFE material modification method, and described polytetrafluoroethylmodified modified filler is polybenzoate, graphite and aramid fiber,
(1) mass percent of its each component is:
Polybenzoate 8～28%
Graphite 1～11%
Aramid fiber 1～11%
The tetrafluoroethylene surplus;
(2) method of modifying is following steps:
A, the tetrafluoroethylene powder is carried out drying back use;
Before b, aramid fiber use, earlier aramid fiber is soaked 10～15 hours with acetone after, respectively boiled 1～1.5 hour with dehydrated alcohol, distilled water respectively, use after putting into oven for drying.Unwashed aramid fiber surface has more dirt settling, and the dirt settling of the fiber surface after cleaning disappears substantially, and fiber surface is Paint Gloss, follow-up fiber surface is carried out chemical treatment, when making it produce active site, can directly activate at fiber surface.Therefore, be combined well with the resin matrix interface for making fiber, fiber is cleaned be necessary.
C, each component set by step after (1) weighing, is put into high-speed mixer, after the high-speed stirring of 2～10min, put into mould coldmoulding, compression rate with 2～5MPa/min is forced into 90～120MPa, and the dwell time is 20～80min, and the demoulding obtains the premolding sample again.The premolding sample is put into the electric furnace sinter molding, and temperature rise rate is 40～80 ℃/h, at 365 ℃～375 ℃ following sintering 5～8h, naturally cools to room temperature with stove then, through the processing of mill decorations, namely obtains the modified materials of polytetrafluoroethyland goods.As preferably, adopt the way compression moulding of unidirectional pressurization in the described step (2).
Polybenzoate is a kind of of thermotropic liquid crystal polymkeric substance, decomposition temperature is up to 530 ℃, but life-time service under 315 ℃, the short-term use temperature is up to 370～425 ℃, be the best kinds of over-all properties such as thermostability, thermal capacity, hardness, self lubricity, wear resistant in present all known macromolecular materials, have fabulous dielectric strength and very little dielectric loss simultaneously, be insoluble to general organic solvent and acid.Polybenzoate is easy to form fento under molten state, be conducive to improve the supporting capacity of matrix material, is conducive to form thin and uniform transfer film on the mating plate surface, and coming off of prevention PTFE zoned crystal improved the wear resisting property of PTFE.Though polybenzoate is filled the back friction and wear behavior and made moderate progress, mechanical property descends to some extent, therefore adds aramid fiber and is improved.
Aramid fiber belongs to organic fibre, it is the abbreviation of aromatic polyamide fibre, be molten a kind of of type liquid crystal that cause, has excellent flowing after the liquid crystalline polymers fusion at high temperature, form thermophoresis, the result of this thermophoresis makes liquid crystalline polymers space along PTFE in the PTFE matrix form fento to moving to flow all around.Under the suitable situation of alloy composition proportioning and sintering temperature, these fentos finally interconnect, in the PTFE matrix, form fine and close and uniform cubic network, these networks the PTFE matrix tightly envelope get up, play reinforcement effect, greatly limit and stoped the band shape wearing and tearing of PTFE, make the wearing and tearing of PTFE become tiny particle ploughing wearing and tearing, thereby improved wear form and the course of PTFE, improved the abrasion resistance properties of PTFE.
Aramid fiber is very soft, can rise directly, be curled in the matrix, has hindered crack propagation; And when fiber break from matrix extract after, owing to friction makes waste of energy, improve impelling strength.
As preferably, described aramid fiber is selected from contraposition aramid fiber (PPTA).Because the PPTA fiber shows lyotropic liquid crystalline, it is a kind of important backbone chain type high molecule liquid crystal, can be scattered in the isotropy matrix material of making excellent property in the matrix better, the mechanical property that its good thermotolerance, erosion resistance are become reconciled has obtained better application in friction sealed matrix material (replacement asbestos).The most outstanding performance of p-aramid fiber is its high strength, high-modulus and outstanding thermotolerance.The weight ratio tensile strength of standard P PTA aramid fiber is 6 times of steel wire, 3 times of glass, 2 times of high-strength nylon industry silk; Its tensile modulus is 3 times of steel wire, 2 times of glass, 10 times of high-strength nylon industry silk; Experience 100hr down at 200 ℃, still can keep 75% of former intensity, experience 500hr down at 160 ℃, still can keep 95% of former intensity.Accordingly, p-aramid fiber is used as lightweight, heat-resisting textile structural material or composite structure strongthener mostly.
Graphite can improve the fragility of matrix material as lubricant, improves toughness, thereby reduces the frictional coefficient of matrix material, improves its mechanical property.
Therefore, the over-all properties of polybenzoate, aramid fiber and graphite-filled modified ptfe is greatly improved with respect to glass fibre.
Compared with prior art, the invention has the beneficial effects as follows: based on the excellent properties of polybenzoate, aramid fiber and graphite, PTFE sealing material with polybenzoate, aramid fiber and the composite filled enhancing of graphite has low wear rate and comprehensive mechanical property excellent characteristics, is desirable senior sealing material.PTFE with its modification makes the anti-attrition lining of working under the high temperature high loading, various seal washers etc., quality and the life-span that can improve component.
Description of drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
Below in conjunction with specific embodiment the present invention is described in further detail.
The key process parameter scope can not obtain the embodiment support in the working method.
Embodiment 1
(1) take by weighing polybenzoate 180 grams: Ekonol 101 SUMITOMO CHEMICAL chemical companies produce, graphite 60 grams: 200 orders, Shanghai gelatinizing plant produced, aramid fiber PPTA (Kevlar1414) 60 gram: my parent form ppta-pulp fibre, pavilion high mountain, Dingxing County science and technology green wood company limited produces, polytetrafluoroethylene PTFE powder 700 grams: 200 orders, the suspension polymerization white powder, Jusheng Fluorine Chemistry Co Ltd, Zhejiang produces.
(2) a, tetrafluoroethylene powder 700 gram is carried out using after the drying treatment.
B, aramid fiber soaked 12 hours with acetone after, boiled respectively 1 hour with dehydrated alcohol and distilled water then, use after putting into oven for drying.
C, then each component is put into high-speed mixer, after the high-speed stirring of 2～3min, put into mould coldmoulding, adopt the way compacting of unidirectional pressurization, compression rate with 3MPa/min is forced into 100MPa, and the dwell time is 30min, and the demoulding obtains the premolding sample again.The premolding sample is put into the electric furnace sinter molding, and temperature rise rate is 60 ℃/h, at 370 ℃ of sintering 6h, naturally cools to room temperature with stove then, through the processing of mill decorations, namely obtains the modified materials of polytetrafluoroethyland goods.
Embodiment 2～4
Each component and the mass percent thereof of polytetrafluoroethylmaterial material modification are as shown in table 1, carry out the modification of polytetrafluoroethylmaterial material according to the method for modifying of embodiment 1.
Table 1: the mass percent of each component in the comparative example 1～4
The performance of table 2: embodiment 1～4 compares:
Comparative example 1～5
Each component and the mass percent thereof of polytetrafluoroethylmaterial material modification are as shown in table 3, carry out the modification of polytetrafluoroethylmaterial material according to the method for modifying of embodiment 1.
Table 3: the mass percent of each component in the comparative example 1～5
Table 4: each embodiment performance compares:
Visible embodiment 1 is preferred embodiment by table 2 and table 4, can obtain having the modified materials of polytetrafluoroethyland of low wear rate and comprehensive mechanical property excellence, is desirable senior sealing material.
Claims (1)
1. a polybenzoate and aramid fiber reinforced TFE material modification method, it is characterized in that: described polytetrafluoroethylmodified modified filler is polybenzoate, graphite and contraposition aramid fiber,
(1) mass percent of its each component is:
Polybenzoate 8 ~ 28%
Graphite 1 ~ 11%
Contraposition aramid fiber 1 ~ 11%
The tetrafluoroethylene surplus;
(2) method of modifying is following steps:
A, the tetrafluoroethylene powder is carried out drying back use;
Before b, contraposition aramid fiber use, earlier the contraposition aramid fiber is soaked 10 ~ 15 hours with acetone after, respectively boiled 1 ~ 1.5 hour with dehydrated alcohol, distilled water respectively, use after putting into oven for drying;
C, with each component set by step after (1) weighing, put into high-speed mixer, after the high-speed stirring of 2 ~ 10 min, put into the way coldmoulding of the unidirectional pressurization of mould employing, compression rate with 2 ~ 5MPa/min is forced into 90 ~ 120MPa, dwell time is 20 ~ 80min, the demoulding obtains the premolding sample again, the premolding sample is put into the electric furnace sinter molding, temperature rise rate is 40 ~ 80 ℃/h, at 365 ℃ ~ 375 ℃ following sintering 5 ~ 8h, naturally cools to room temperature with stove then, through the processing of mill decorations, namely obtain the modified materials of polytetrafluoroethyland goods.
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| CN112521703B (en) * | 2020-11-03 | 2022-11-04 | 上海工程技术大学 | Method for preparing modified aramid pulp/PTFE composite material by supercritical carbon dioxide polymerization |
| CN113248852B (en) * | 2021-07-15 | 2021-09-21 | 北京石墨烯技术研究院有限公司 | Modified polytetrafluoroethylene composite material, preparation method thereof and sealing element |
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| CN101914254B (en) * | 2010-03-15 | 2013-03-13 | 浙江吉利汽车研究院有限公司 | Polytetrafluoroethylene composite material for crankshaft oil seal and preparation method thereof |
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