CN1283717C - Fusible body formed polytetrafluorethylene - Google Patents

Fusible body formed polytetrafluorethylene Download PDF

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CN1283717C
CN1283717C CN 99119799 CN99119799A CN1283717C CN 1283717 C CN1283717 C CN 1283717C CN 99119799 CN99119799 CN 99119799 CN 99119799 A CN99119799 A CN 99119799A CN 1283717 C CN1283717 C CN 1283717C
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ptfe
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composition
polyarylene ether
ether ketone
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CN1284519A (en
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J·拉希亚尼
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EIDP Inc
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EI Du Pont de Nemours and Co
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Abstract

The present invention provides a soluble body shaping composition containing at least 50 wt% of polytetrafluoroethylene, wherein the composition contains poly arylidene ether ketone and a part which is determined by specific situations, and the polytetrafluoroethylene is PTFE ultrafine powder.

Description

Fusible body formed tetrafluoroethylene
Technical field
The present invention relates to the making method of polyetetrafluoroethycomposition composition and goods thereof.
Background technology
As everyone knows, polytetrafluoroethylene (PTFE) does not have the melt forming performance, and this is that for example its viscosity is at least 10 in the time of 380 ℃ because it has very high melt viscosity 8PaS is so that PTFE can't flow under melting condition.Therefore can't be by the melt extrusion method of forming commonly used, comprise that injection moulding makes PTFE.On the contrary, developed the forming method that does not comprise melt flow.For the PTFE of fine powder form when wherein PTFE stands to shear (but be fibrillation), PTFE is extruded by pasty state, and this is a kind of low temperature that carries out on the basis of fine powder type PTFE and oil mixture (being lower than 75 ℃) extrusion.Granular PTFE prepares by compression moulding, and this method comprises, with the particles filled mould of refrigerative PTFE, then with the drift extrusion and add the thermosetting mould.Needing to remove lubricant after pasty state is extruded is one of problem relevant with the pasty state extrusion molding.The compression moulding of granular PTFE is confined to simple shape.Therefore any form of PTFE all can not be used injection molding, when the shape of PTFE goods demand complexity, has to the pressing mold module of PTFE is carried out machining.
Summary of the invention
The invention provides polyetetrafluoroethycomposition composition, therefore said composition can pass through the injection molding melt forming by extruding.Said composition contains the tetrafluoroethylene of 50% (weight) at least, and wherein the melt viscosity of at least 20% (weight) is at least 10 8PaS, surplus is a polyarylene ether ketone, total amount is 100% (weight) after these two kinds of resin-bonded.
The present invention relates to:
1. fusible body formed composition, said composition contains at least 50 weight % tetrafluoroethylene and polyarylene ether ketones, and the described tetrafluoroethylene of at least 20 weight % has under 380 ℃ at least 10 8The melt viscosity of Pas, described tetrafluoroethylene is a fine powder type, and described composition contains the described polyarylene ether ketone of 20-50 weight %.
2. above-mentioned 1 fusible body formed composition, wherein said polyarylene ether ketone are PEKK.
3. fusible body formed composition, said composition contains at least 50 weight % tetrafluoroethylene and at least 4 weight % polyarylene ether ketones, and the described tetrafluoroethylene of at least 20 weight % has under 380 ℃ at least 10 8The melt viscosity of Pas, described composition contain the consumption that can make described polyarylene ether ketone and are reduced by at least 40% the superfine powder of polytetrafluoroethylene with fluidity of molten.
4. above-mentioned 3 fusible body formed composition, wherein, based on tetrafluoroethylene and polyarylene ether ketone component in conjunction with weight, the consumption of described polyarylene ether ketone is reduced to only 4 weight %.
5. above-mentioned 3 fusible body formed composition, the amount of described ultrafine powder are the 20-80% of described tetrafluoroethylene and ultrafine powder gross weight.
6. above-mentioned 5 fusible body formed composition, wherein said superfine powder of polytetrafluoroethylene is 50-1 * 10 372 ℃ of melt viscosities of measuring down 5Pas.
7. the fusible body formed composition of claim 3, wherein said polyarylene ether ketone is a PEKK.
8. melt extrusion method comprises any one fusible body formed composition of the above-mentioned 1-7 of melt extrusion.
9. above-mentioned 8 melt extrusion method, wherein melt extrusion comprises injection molding.
Embodiment
When extruding with melt form, composition is matrix with PTFE, and polyarylene ether ketone disperses wherein to solidify the fine particulate form (domain structure) of coming out from melt.Therefore, the moulded product of melt forming composition has most of characteristics of PTFE, for example, and high use temperature, unreactiveness, and oilness (low friction).As will be explained hereinafter, composition can contain the PTFE of at least 90% (weight), and this further impels the attribute of moulded product similar to pure PTFE.
As everyone knows, polyarylene ether ketone is the resin that gang comprises following polymkeric substance: have the polyetherketone of following repeating unit,
Polyether-ether-ketone with following repeating unit,
Figure C9911979900042
With PEKK with following repeating unit,
Figure C9911979900043
Wherein, the arylidene between the ketone group of PEKK is normally right-and-the arylidene mixture, derived from for example isophthaloyl halogen and terephthaloyl halogen, be present in the repeating unit that constitutes resin.These resins are known as PEK usually respectively, PEEK, and PEKK, and be disclosed in following one or the multinomial United States Patent (USP): US 3,065,205, US 3,441,538, and US 3,442,857, US 5,357, and 040, US 5,131,827, and US 4,578,427, US3,516,966, US 4,704,448 and US 4,816,556.This polyarylene ether ketone generally has 300 ℃ fusing point, high molecular, high strength and the high-modulus characteristic of being not less than of engineering plastics.For example 30 ℃ is that the logarithmic viscosity number of this resin can reach and be at least 0.4 in the solution of 0.5% (weight) of solvent with the vitriol oil.Preferred PEKK, because it has low melt viscosity and low speed crystallization, this is convenient to mixing of resin and PTFE, and provides fluidity of molten for resulting composition.PEKK contains usually derived from 90: 10 to 30: 70, more generally be 80: 20 to 60: 40 terephthaloyl (T) halogen and the unit of isophthaloyl (I) halogen, along with T unit ratio reduces and the increase of I unit ratio, the degree of crystallinity of PEKK reduces, up to 60: 40, the crystallization of PEKK is slowly to except having fusing point, and it more resembles a kind of amorphous polymer.The present invention is applicable to whole poly (arylene ether) ketone resins, that is to say, they all give PTFE with the melt forming performance.
PTFE also is a kind of known resin.Preferred fine powder type, this type is prepared by the aqueous dispersion polymerization method.But product P TFE fine powder is the resin of fibrillation.A kind of U.S. Pat 4,952 that for example is disclosed in 636, also is also to can be used for the present invention by the carefully fibrillation of aqueous dispersion polymerization method preparation, the PTFE resin of non-melt forming.As U.S. Pat 3,142, PTFE can be the homopolymer of proplast or modification as described in 665, promptly contains on a small quantity as be less than the homopolymer of the comonomer of 0.5% (mol), and this comonomer has improved the film forming properties of resin.PTFE has at least 10 usually in the time of 380 ℃ 8The melt viscosity of PaS.
The part that PTFE and PEKK component can be used as extrusion process is by melt-mixing, and perhaps pre-mixing is carried out melt-mixing subsequently under the temperature of polyarylene ether ketone fusing at least.Under the injection molding situation, preferred composition at first uses the twin screw extruder that high scissors screw rod for example is installed to carry out melt-mixing, forms granular molding (pellet), casting then, and this process promotes polyarylene ether ketone zone uniform distribution in the PTFE matrix.In general, melt mix temperature is at least at 350 ℃.With this understanding, polyarylene ether ketone make the composition fluidify and in the PTFE component with thin melt zone uniform distribution, make that composition can be by melt extrusion.Extruded product can be final moulded product, and as injection-molded product or extruded tube, sheet material or coating also can be chopped into the mold pressing particle and be used for the melt of required goods subsequently.Show uncompatibility between these two kinds of resins as the existence of the polyarylene ether ketone component of discrete particle (zone) in the PTFE matrix.Yet the pressing of being made by the present composition all has good character.
When carrying out mold pressing, when PTFE is maintained the matrix phase, exist some amount to give the polyarylene ether ketone of composition effectively in the composition with melt extrusion.When PTFE was fine powder type, the polyarylene ether ketone of 20% (weight) that only needs composition was to give the composition that obtains with melt forming, and therefore, composition contains 20-50% (weight), the polyarylene ether ketone of preferred 20-30% (weight).Except as otherwise noted, the weight percentage of component is based on the gross weight of PTFE and polyarylene ether ketone component.
Find that also when keeping melt forming, the quantity of polyarylene ether ketone can reduce in the composition.In composition, add the PTFE ultrafine powder and make that obtaining such result becomes possibility, so that only use the polyarylene ether ketone of about 4% (weight) just to be enough to give composition with melt extrusion, wherein 4% (weight) be based on PTFE and polyarylene ether ketone component in conjunction with weight.In this embodiment, the PTFE component had both contained high melt viscosity (non-melt forming) PTFE, contained the PTFE ultrafine powder again.The PTFE ultrafine powder is not only the PTFE fine powder.On the contrary, the PTFE ultrafine powder is the homopolymer of proplast or modification, this homopolymer has than the much lower molecular weight of for example above-mentioned PTFE fine powder of conventional high melt viscosity PTFE, this homopolymer makes ultrafine powder itself have fluidity of molten, at 372 ℃, according to as U.S. Pat 4,380, the melt viscosity of the ultrafine powder of the 618 described ASTM D-1239-52T method tests that changed is 50-1 * 10 5PaS.Preferred PTFE ultrafine powder melt viscosity in the time of 372 ℃ is 100-1 * 10 4PaS." encyclopedia of chemical technology " the 4th edition 637-639 page or leaf of publishing (1994) the 11st volumes by John Wiely and Sons at Kirk-Othemer, and at article " PTFE ultrafine powder " the Kunstoffe Genman of H-J Hendriock Plastics, the 76th phase 920-926 page or leaf (1986) all further describes the PTFE ultrafine powder.The ultrafine powder that these publications are put down in writing is that the PTFE radiation degradation by polymerization or high molecular (high melt viscosity) gets.Direct polymerization obtains ultrafine powder and for example is disclosed among the PCT WO95/23829, and wherein ultrafine powder is called as low melt viscosity PTFE.Although the PTFE ultrafine powder has fluidity of molten, because the lower molecular weight of PTFE ultrafine powder makes products therefrom not have practical intensity, so itself neither melt forming.Therefore the bead that obtains in the melt flow rate (MFR) test of carrying out for definite melt viscosity is brittle, to such an extent as to the slightest bending just can make its fracture.
If use, the amount of PTFE ultrafine powder preferably will make the consumption of the required polyarylene ether ketone of PTFE composition melt forming reduce at least 40% effectively in the composition.Therefore, because the existence of ultrafine powder, the composition when few polyarylene ether ketone to 4% or 5% (weight) just is enough to make melt extrusion has melt forming.When injection molding, preferably the polyarylene ether ketone of about at least 10% (weight) is used for increasing fluidity of molten.When PTFE was fine powder, composition can contain the polyarylene ether ketone of 4-10% (weight), and surplus is PTFE fine powder and PTFE ultrafine powder, and the consumption of ultrafine powder all is to make composition have melt forming effectively in either case.When the PTFE ultrafine powder is used for composition, its consumption is generally ultrafine powder combines back weight with PTFE (high melt viscosity) 20%-80% (weight), wherein there is the 20% preferred high melt viscosity PTFE of at least 25% (weight) (based on the PTFE gross weight) at least in preferred 30-75% (weight).Certainly, the whole PTFE in the PTFE/ poly (arylene ether) alcohol/ketone mixtures can be high molecular PTFE.
The combination of the PTFE of high melt viscosity and PTFE ultrafine powder provides a kind of goods, and wherein, the PTFE of two kinds of forms is mixtures that the PTFE resin allows the people can not differentiate, and forms polyarylene ether ketone distribution matrix wherein.The PTFE resin has very high thermostability and intensity, therefore is not subjected to polyarylene ether ketone and the remarkably influenced partly of PTFE ultrafine powder in the PTFE resin.
The present composition can contain other compositions, for example for the pigment of composition colouring or for example be fibrous or other granular glass, and carbon or fragrant acid amides filler.Polyarylene ether ketone helps the dispersion of filler in the PTFE matrix.When filler existed, its quantity was PTFE and the filler 0.5-30% (weight) in conjunction with weight.
The melt extrusion of the present composition can utilize with fusible body formed fluoropolymer for example the identical method extruded of TEFLON  RFA fluoropolymer resin (Dupont) implement, be extruded into various shape such as sheet, tubulose and coating matrix are as the insulation layer on the wire.Equally, injection molding can be with implementing with the method that for example injection molding of PFA fluoropolymer is identical when temperature is 330-370 ℃.The PTFE fine powder is usually clinkering behind non-melt forming, but is extruded by pasty state except the situation of fine powder gained band.In the melt forming of the present composition, for make pressing have required whole needed all, be exactly that melt in moulding process exposes.If want bigger intensity, can be by clinkering subsequently.
In the following embodiments; the mixture melt forming of polyarylene ether ketone and PTFE is tension test bar (" dog bone " shape; long 8-1/2 inch (21.6cm); the pilot region of wide 0.5 inch (1.27cm); thick 0.125 inch (0.32cm)), use be 6 ounces of (170g) injectors, have following temperature distribution in screw rod/plunger compartment: rear portion=370 ℃; middle=380 ℃, anterior=380 ℃.Screw speed is 120rpm, and back pressure is 50Psi (0.35MPa).About 110 ℃ of molding temperature, clamping cycle is 20sec/20sec.The PEKK resin that uses among the embodiment is by U.S. Pat 4,816, the method preparation of 556 people such as () Gay.
Embodiment 1
In this embodiment, PTFE is a TEFLON  fluoropolymer resin, and (melt viscosity is greater than 1 * 10 for grade 60 (Dupont) 8PaS) and polyarylene ether ketone be that T and I unit ratio are 80: 20 PEKK, itself tensile modulus of (test bar) is 530ksi (3657MPa).Annotate: 1Ksi=1000Psi.With PTFE and PEKK dry mixed, each composition accounts for 50% of total mixture.Before injection-molded goods comprise the tension test bar, mixture is carried out melt-mixing in injector then.The tensile modulus that the mixture test bar shows is 375ksi (2588MPa).Tensile modulus utilizes ASTM D638 method to record, and this method also is used to obtain the test result of other tensile moduluses that this paper puts down in writing.Present embodiment shows the melt forming of PTFE, and wherein PEKK exists with maximum.
Embodiment 2
In this embodiment, use PTFE and the polyarylene ether ketone identical with embodiment 1.In this embodiment, part PEKK is replaced by the PTFE ultrafine powder, ZONYL  fluorochemical additive particularly, and (MFR17g/10min, melt viscosity 3 * 10 in the time of 372 ℃ for grade MP1600 (Dupant) 3PaS).Contain 20% (weight) PEKK, the tensile modulus of the injection molding test bar of the mixture of 50% (weight) PTFE and 30% (weight) MP1600 is 201ksi (1387MPa).Only contain 10% (weight) PEKK, the tensile modulus of the injection molding test bar of the mixture of 30% (weight) PTFE and 60% (weight) MP1600 is 283ksi (1953MPa).The combination of fluoropolymer (PTFE and MP1600) accounts for 80% and 90% (weight) of these mixtures respectively, makes them have the characteristic of high fluoropolymer, but has the advantage of melt forming.The test bar molded by MP1600 itself do not have tensile modulus, because break when grip of testing machine is caught when they are stretched, this low strength is attributable to the lower molecular weight of this PTFE ultrafine powder.Surprisingly, the existence of MP1600 does not destroy the tensile strength of mixture in the mixture.More surprisingly, it is bright that the mixture with high level MP1600 has higher stretching die.The PTFE test bar can not carry out injection molding by itself, because the high melt viscosity of this resin has stoped such melt forming.The tensile modulus that provides by the controlled trial bar that PTFE clinker stripping flakiness is got is 80ksi (552MPa).
Embodiment 3
The PTFE of Shi Yonging is identical with embodiment 1 in this embodiment, and the polyarylene ether ketone that uses is T and I unit weight ratio is 60: 40 PEKK.This PEKK also contains 10% (weight) TiO 2Pigment, tensile modulus are 495ksi (3416MPa).Contain 20% (weight) PEKK/TiO 2Mixture, the tensile modulus of the test bar of the mixture of 30% (weight) PTFE and 50% (weight) MP1600 is 249ksi (1718MPa).

Claims (9)

1. fusible body formed composition, said composition contains at least 50 weight % tetrafluoroethylene and polyarylene ether ketones, and the described tetrafluoroethylene of at least 20 weight % has under 380 ℃ at least 10 8The melt viscosity of Pas, described tetrafluoroethylene is a fine powder type, and described composition contains the described polyarylene ether ketone of 20-50 weight %.
2. the fusible body formed composition of claim 1, wherein said polyarylene ether ketone is a PEKK.
3. fusible body formed composition, said composition contains at least 50 weight % tetrafluoroethylene and at least 4 weight % polyarylene ether ketones, and the described tetrafluoroethylene of at least 20 weight % has under 380 ℃ at least 10 8The melt viscosity of Pas, described composition contain the consumption that can make described polyarylene ether ketone and are reduced by at least 40% the superfine powder of polytetrafluoroethylene with fluidity of molten.
4. the fusible body formed composition of claim 3, wherein, based on tetrafluoroethylene and polyarylene ether ketone component in conjunction with weight, the consumption of described polyarylene ether ketone is reduced to only 4 weight %.
5. the fusible body formed composition of claim 3, the amount of described ultrafine powder is the 20-80% of described tetrafluoroethylene and ultrafine powder gross weight.
6. the fusible body formed composition of claim 5, wherein said superfine powder of polytetrafluoroethylene is 50-1 * 10 372 ℃ of melt viscosities of measuring down 5Pas.
7. the fusible body formed composition of claim 3, wherein said polyarylene ether ketone is a PEKK.
8. melt extrusion method comprises any one fusible body formed composition of melt extrusion claim 1-7.
9. the melt extrusion method of claim 8, wherein melt extrusion comprises injection molding.
CN 99119799 1999-08-16 1999-08-16 Fusible body formed polytetrafluorethylene Expired - Fee Related CN1283717C (en)

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