CN1162328A - Melt-processable fluoroplastic - Google Patents

Abstract

The invention provides a melt-processable fluoroplastic composition comprising a blend of a melt-processable thermoplastic fluoropolymer component of interpolymerized units derived from 1,1-difluoroethylene and at least one ethylenically-unsaturated, copolymerizable, fluorinated comonomer, and a hydrocarbon polymer component comprising poly(oxyalkylene). The composition is useful for making shaped articles including tubing or film.

Description

The fluoroplastics of melt-processable

The present invention relates to thermoplastic fluoropolymer composition and preparation thereof and application, and adopt moulded products such as film and the tubing of melt-processed as extruding described preparation of compositions.On the other hand, the present invention relates to improve the flowing property of the thermoplastic fluoropolymer composition that is used to make extrusion moulding product, in order that, make these extrusion moulding products with the metal defects such as the melt fracture of fast rate of extrusion, minimizing.

The commodity fluoropolymer than new class be: tetrafluoroethylene, R 1216 and the combination in varing proportions of 1.1-difluoroethylene comonomer obtain thermoplasticity, the chemical resistant properties of different melting points scope, the terpolymer of thermally-stabilised optical transparency low-permeability.These fluoropolymers are flexible better, can than other fluoroplastics of great majority as melt-processed under the low temperature of poly-vinylidene fluoride and ethylene-tetrafluoroethylene copolymer.This serial fluoropolymer is sold with " 3M THV Fluoroplastics " by 3M company, and it can be used for preparation, for example: mo(u)lded item and extrusion film, tubing and section bar.Because these fluoropolymers are flexible better than the fluoroplastics of other melt-processable, bending or moulding easily, and have low-permeability, found in automotive fuel pipeline, vapor recovery pipeline and charging or exhaust hose special purpose as permeation barrier.Though these fluoroplastics have many advantageous characteristic and processing characteristics, but we find, under some melt-processed condition, some fluoroplastics forms surface irregularity and gets very unfavorable extrudate, present melt fracture when perhaps being irregularly shaped on the surface, this is called " shark skin spot " in polymer melt technology, referring to, for example, Brydson, J.A. work " flow properties of polymer melts matter " (" Folw Properties ofPolymer Melt ", Van Nostrand Reinhold Co., New York, 1970) the 5th chapter.It is crucial burning line flexible pipe or conduit for the use of this class moulded products that this defective surface makes this class extrudate not too be suitable for use as smooth surface.Specifically, slipperiness is that conduit guarantees the prerequisite that liquid evenly flows through and allows wire or the level and smooth insertion of detector.In the burning line flexible pipe, for forming the liquid laminar flow and obtaining low permeability, smooth surface is preferred.

We find, by with 1, the thermoplastic fluoropolymer of the melt-processable of 1 difluoroethylene and one or more ethylene linkage unsaturated comonomers, for example above-mentioned 3M THVFluoroplastics, with a small amount of some polyoxyalkylene polymers, polyethylene glycol blending for example, the blend of gained can carry out melt-processed with the flowing property that improves as lower shear-stress under quite low melt temperature, the extrudate that has required smooth-flat-surface with easy formation, this makes them can be in the place that requires or need these performances and fluoropolymer proper property, as burning line flexible pipe or tubing, obtain use or improve its use status.These improvement need not chemical structure, the raising melt processing temperature of (for example) modified fluoride-containing polymkeric substance or extrude (these measures are taked for reducing melt fracture sometimes) under lower linear velocity or shearing rates just can obtain.

According to an aspect of the present invention, a kind of fluoroplastic compositions of melt-processable is provided, it is the blend of main amount with fluoropolymer component (a) that said composition comprises a kind of, the amount that is fluoropolymer is greater than 50% of composition weight, fluoropolymer component is a kind of thermoplastic fluoropolymer of melt-processable, but its copolymerization units derived from vinylidene fluoride and the undersaturated copolymerization fluorinated comonomers of at least a ethylene linkage as (1) with general formula R _fCF=CF ₂Expression fluoridize alpha-olefin, R in the formula _fIt is the perfluoroalkyl of H, F, Cl or 1 to 8 preferred 1 to 3 carbon atom, (2) optional a small amount of (being below 50% of described fluoropolymer weight) contain 1 to 4 carbon atom for example perfluor (alkyl vinyl ether) as perfluor (methylvinylether), and/or lower molecular weight alpha-olefin such as ethene and propylene; In the described fluoropolymer that exists with the base-material form, disperse a small amount of (below 20% of described composition weight) hydrocarbon polymer component (b), it comprises polyoxyalkylene polymers such as the polyoxyethylene glycol that is dispersed in the described fluoropolymer base-material.

On the other hand, the invention provides a kind of method of moulded products of fluoroplastic compositions of processing this class melt-processable.This method comprises following component blend, (a) the thermoplastic fluoropolymer component of the melt-processable of more amount, its copolymerization units is derived from 1, but the undersaturated copolymerization fluorinated comonomers of 1-difluoroethylene and at least a ethylene linkage and (b) comprise the hydrocarbon polymer component of polyoxyalkylene polymers on a small quantity; Blend melt-processed with gained is shaped to described goods again.

The hydrocarbon polymer component of using as blend component in the fluoroplastic compositions of preparation melt-processable of the present invention is nonfluorinated polymers (it is described as, and " hydrocarbon " distinguishes it and fluoropolymer blend component).The hydrocarbon polymer component is fluid at the melt processing temperature of fluoropolymer under as 180～280 ℃, and fluoropolymer component be the solid room temperature as 20 ℃ under, be liquid, or solid preferably.Hydrocarbon polymer component and fluoropolymer component are immiscible, this is for example checked by optical microphotograph by following, perhaps by not containing when composition when making its painted certain batching as filler, the outward appearance of the extrudate of this blend composition is, and muddy, white or opaque shape proves.Extrudate has kept the character of fluoropolymer component basically, the thermostability under 220～280 ℃ for example, but compare with the extrudate of fluoropolymer, show melt-processible or the extrusion performance improved, because, can be for given extrudate shape under higher productivity or the very fast speed and under the much lower more high shear rate of shearing stress, extrude the extrudate of blend composition of the present invention, and the extrudate surface quality is good, smooth especially, in other words, there are not deleterious metal defects or melt fracture comparatively speaking as " shark skin spot ".

The above-mentioned fluoropolymer that uses among preferred the present invention is those hydrogenous thermoplasticss that the ASTMD1238 melt index of measurement under 265 ℃ of 5kg loads is lower than 1000 Grams Per Minutes, and it can melt extrude under 250 ℃.

For preparation blend of the present invention, preferably contain at least 5% weight from 1,1-difluoroethylene deutero-unit and 25% weight are above from unitary those fluoropolymers of the mixture deutero-of tetrafluoroethylene and R 1216, the fluorine content of fluoropolymer is below 75% weight like this, and is the thermoplastics that melting is extruded.

The preferred fluorine polymkeric substance that uses among the present invention is by 30～70% weight, the tetrafluoroethylene of preferred 35～65% weight, 10～30% weight, the R 1216 of preferred 15～25% weight and 10～50% weight, the vinylidene fluoride copolymerization of preferred 15～45% weight obtains.A subclass that is used to prepare the fluoropolymer of blend of the present invention is the fluoroplastics that contain derived from the copolymerization units of the raw material monomer of 45～65% weight tetrafluoroethylene, 10～20% weight R 1216s and 20～35% weight vinylidene fluorides.United States Patent (USP) 4,670, the fusing point that described this class fluoropolymer of 503 people such as () Newmann adopts differential scanning calorimeter to measure is 130～170 ℃, ASTMD 1238 melt indexs of measuring under 265 ℃, 5kg load are 50～250 grams/10 minutes.Operable commodity fluoropolymer is above-mentioned THVFluoroplastics, is described in product announcement 98 0211-7703-9 (103.02) RI of 3M company, 98 0211-7010-9 ,-7011-7 ,-7012-6 ,-7013-3 ,-7014-1 and-8100-7 in.ASTMD 3418 melting ranges of THV200 level, 400 grades of THV and 500 grades of fluoroplastics of THV are respectively 115～125 ℃, 150～160 ℃ and 165～180 ℃, and the ASTMD1238 melt flow index is respectively 20,10 and 10 under 265 ℃ and 5kg.Narration at the THV Fluoroplastics described in the described product announcement is hereby incorporated by.

The polyoxyalkylene polymers of Shi Yonging can comprise polyoxyalkylene polyol and derivative thereof in the present invention.This class polyoxyalkylene polymers can be represented with following general formula:

A[(OR ¹) _xOR ²] _yIn the formula: A is the residue that does not contain active hydrogen that contains the low molecular weight initiator organic compound of a plurality of active hydrogen atoms (for example 2 or 3), for example poly-hydroxy paraffinic hydrocarbons or polyether glycol such as ethylene glycol, glycerol, 1,1,1-TriMethylolPropane(TMP) and polypropylene glycol; Y is 2 or 3; (OR ¹) _xBe the polyoxyalkylene chain that comprises many oxyalkylene groups, (OR ¹), R wherein ¹Base can be identical or different, is selected from C ₁～C ₅Alkylidene group, preferred C ₂Or C ₃Alkylidene group; X is the number of oxyalkylene units in the described chain, and described polyoxyalkylene chain can be homopolymer chain such as polyoxyethylene or polyoxypropylene, and the chain of (being the xenogenesis mixture) oxyalkylene group that perhaps can be random distribution is as-OC ₂H ₄-and-OC ₃H ₆-unitary multipolymer, or contain the alternately block of repeated oxidation thiazolinyl or main chain segmental chain as comprising-(OC ₂H ₄)- _aWith-(OC ₃H ₆)- _bThe polymkeric substance of block, a+b=5 to 5000 or higher wherein, for example 20,000 or higher, be preferably 10～500.R ²Be H or organic group such as alkyl, aryl or its combination as aralkyl or alkaryl, can also contain O or N heteroatoms.For example: R ²Can be methyl, butyl, phenyl, benzyl and acyl group such as ethanoyl (CH ₃CO-), benzoyl (C ₆H ₅CO-) and stearyl-(C ₁₇H ₃₅CO-).

Typical polyoxyalkylene polymers derivative can comprise the polyoxyalkylene polyol derivative, and wherein terminal hydroxy group has partly or entirely changed into ether derivant, and for example methoxyl group, or ester derivative is as stearate group (C ₁₇H ₃₅COO-).Other useful polyoxyalkylene derivatives are polyester, for example the polyester that is prepared by dicarboxylic acid and poly suboxygen alkyl glycol.Preferably, the main part by weight of polyoxyalkylene polymers derivative is the oxyalkylene recurring group, (OR ¹).

Described polyoxyalkylene polyol and derivative thereof can be at room temperature to be at least approximately 200 for solid, molecular weight, and preferred molecular weight is about 400～20,000 or higher, for example 200,000 or higher those.

The polyoxyalkylene polyol of Shi Yonging comprises and can use general formula H (OC in the present invention ₂H ₄) _nThe polyoxyethylene glycol that OH represents, n is about 15 to 3000 in the formula, those that sell with trade mark Carbowax for example are as Corbowax ^TMPEG 8000, herein n be about 181 and sell with trade mark Polyox those, as Polyox ^TMWSR N-10, n is about 2272 herein.

Above-mentioned two or more polyoxyalkylene polymers can be used as blend component (b) or one or more this base polymers with the olefin polymer of ethene or propylene as blend component (b), every kind of polymkeric substance is, for example, 5～95% weight of hydrocarbon blends component (b).

Olefin polymer can be the homopolymer of ethene or propylene, or their mutual multipolymers, or two of in them one or they and the another kind of ethylene linkage unsaturated comonomer multipolymer of alpha-olefin such as 1-octene for example.The melt viscosity that preferred these optional olefin polymers that use as blend component (b) with polyoxyalkylene have and the melt viscosity of fluoropolymer component (a) are more or less the same or are roughly the same, and described olefin polymer also is dispersed in the fluoropolymer matrix.

The small amounts of olefins polymkeric substance that uses as the hydrocarbon blends component with polyoxyalkylene can be the polymkeric substance that ethene or propylene homopolymerization obtain in the present invention, or their mutual copolymerization or one or their two polymkeric substance that obtain with one or more high alpha-olefin copolymerization in them, high alpha-olefin be up to can with this class alkene about 30% weight of the undersaturated comonomer of one or more ethylene linkages of vinyl ester compound such as vinyl acetate copolymerization for example, but preferred 20% weight or lower.Described alkene can be with general structure CH ₂=CHR represents that R is hydrogen or contains no more than 10 carbon atoms, the alkyl of preferred 1～6 carbon atom in the formula.Typical alkene is ethene, propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene and 1-octene.Can be vinyl ester with the typical monomer of described olefin-copolymerization, for example vinyl-acetic ester, propionate, vinyl butyrate, vinyl chloroacetate and chloropropionic acid vinyl acetate; Vinyl alcohol; Vinylformic acid and alpha-alkyl vinylformic acid and alkyl ester thereof, acid amides and nitrile, for example vinylformic acid, methacrylic acid, ethylacrylic acid, methyl acrylate, ethyl propenoate, N,N-DMAA, Methacrylamide and vinyl cyanide; Vinyl aromatic compounds, for example vinylbenzene, O-methoxy vinylbenzene, to methoxy styrene and vinyl naphthalene; Vinyl halide and 1,1-acetylenedihalide such as vinylchlorid, vinylidene chloride, 1,1-sym-dibromoethane; The alkyl ester of toxilic acid and fumaric acid and its acid anhydride such as dimethyl maleate, ethyl maleate and maleic anhydride; Vinyl alkyl ethers such as vinyl methyl ether, EVE, vinyl isobutyl ether and 2-chloroethyl vinyl ether; Vinyl pyridine; The N-vinylcarbazole; The N-vinyl pyrrolidone; With dienes such as 1,3-butadiene.Olefin polymer also can be metal-salt or its blend that contains the described olefin copolymer of free carboxy acid's base.Can be used to provide the metal example of the salt of described carboxylic acid polyalcohol is monovalence, divalence and trivalent metal such as sodium, lithium, potassium, calcium, magnesium, aluminium, barium, zinc, zirconium, beryllium, iron, nickel and cobalt.The representative instance of the olefin polymer that uses among the present invention is polyethylene, polypropylene and ethene and propylene is mutual and/or the multipolymer of 1-butylene, 1-hexene, 4-methyl-1-pentene or 1-octene.

The typical blend of the olefin polymer of using among the present invention is polyethylene and polypropylene, new LDPE (film grade) and high density polyethylene(HDPE) and polyethylene and the blend that contains the olefin copolymer of the copolymerisable monomer described, that some of them have above been stated, this class olefin copolymer such as ethylene and acrylic acid copolymer, ethene and methyl acrylate copolymer, ethene and ethyl acrylate copolymer, ethene and vinyl acetate copolymer and ethene, vinylformic acid and vinyl acetate copolymer.

Preferred olefin polymer is following thermoplastic polymer, i.e. the multipolymer of the homopolymer of ethene and ethene and 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene and propylene.

The commodity olefin polymer that can use in the present invention comprises the Escorene of Exxon (Exxon) chemical company ^TMLL-3001.00, LL-5202, LD411.09 and LD760.36 polyethylene, Iotek ^TM7030 ionomers and Escor ^TMThe ATX310 acid terpolymer; The ER1833 polyethylene of Chevron chemical company; The Novapol of Novacor chemical company ^TMTF 0119F polyethylene; The Dowlex of road (Dow) chemical company ^TM2047 polyethylene; The Marlex of Philips (Phillips) 66 companies ^TMThe HMN4550 polyethylene; Fina oil and the 3374X polypropylene of chemical company and the Polysar of the Polysar of Miles company rubber branch ^TMEPM306 and EPDM345 ethylene-propylene rubber(EPR).

The melt flow index of preferred olefin polymers is 0.01～1000 gram/10 minutes, and more preferably 0.1～100 gram is/10 minutes, measures under 190 ℃ and 2.16kg according to ASTM D1238.Preferred olefin polymer is a polyethylene.

Preferably the melt viscosity of the melt viscosity of the olefin polymer that uses with polyoxyalkylene polymers and fluoropolymer is more or less the same or is roughly the same.Can select olefin polymer to make its melt viscosity and the ratio of the melt viscosity of fluoropolymer is 0.01/1 to 10/1, more preferably 0.1/1 to 1/1.For this ratio, the viscosity of two kinds of polymkeric substance is measured under typical the same terms of component (a) and blend melt-processable (b).

Some blend of component can require a kind of concrete hydrocarbon polymer component (b) more than the amount of other hydrocarbon polymers, so that extrudate has smooth surface.The application of or transparent extrudate colourless for needs, some hydrocarbon polymer are as containing from the olefin polymer of polar comonomers deutero-polar group, or those low polymkeric substance of thermostability can give extrudate unacceptable color.

With the lower limit amount of the hydrocarbon polymer component (b) of fluoropolymer component (a) blend normally, do not compare with the identical fluoropolymer of hydrocarbon component (b) blend with having, the rate of extrusion that increases blend does not have the amount of table of discovery plane defect in the extrudate of blend.Usually, the amount of hydrocarbon polymer component is about 0.01～10% weight of fluoropolymer-hydrocarbon polymer blend weight, more preferably about 0.05～5% weight, most preferably from about 0.1～1% weight.The concentration that increases hydrocarbon polymer generally makes the transparency of extrudate reduce.

Fluoropolymer and hydrocarbon polymer component (a) and blend (b) can adopt the normally used mixing method preparation of plastics industry, for example the compounding roller refines machine, Banbury Banbury mixer or melting extruder, and hydrocarbon polymer is evenly distributed among the fluoropolymer in these equipment.Fluoropolymer and polyoxyalkylene polymers can be to use as powder, sheet stock or particulate form.Married operation can carry out easily being higher than under the temperature of melting point polymer.Also two kinds of polymkeric substance can be done with solid particles and be mixed, make blend make the hydrocarbon polymer uniform distribution then by the twin screw melt extruder.

The melt-blended mixtures of resulting fluoropolymer and hydrocarbon polymer can granulation or in other words is ground into required size of particles; be fed to forcing machine; forcing machine is generally single screw extrusion machine; fusing point, melt viscosity and thermostability according to blend; for example under 180～280 ℃, the melt-processed blended mixts.Can be used in the dissimilar forcing machine of extruding fluoroplastic compositions of the present invention and be described in for example Rauwendaal, the 23rd～48 page of C. work " polymer-extruded " (" Polymer Extrusion " Hansen Publishers, 1986th).

The extruder die head design can change with the extrudate of require preparation.For example: annular die head can be used for extruding the tubing that is used to make the burning line flexible pipe, and as United States Patent (USP) 5,284,194 (people such as Noone) are described, are hereby incorporated by.

The fluoroplastics blend composition can contain traditional proportioning such as oxidation inhibitor, pigment and filler such as titanium dioxide, carbon black and silicon-dioxide.

Embodiment

Following embodiment illustrates fluoroplastic compositions of the present invention and extrudate and advantage thereof, for example in the embodiment of this invention shearing stress reduce greatly and the extrudate appearance that obtains quite desirable.

Employed fluoroplastics are commodity 3M THV 500 Fluoroplastic among these embodiment, and it has the comonomer raw material deutero-copolymerization units from about 20% weight vinylidene fluoride, 60% weight tetrafluoroethylene and 20% weight R 1216.

The polyoxyalkylene polymers that these embodiment use is the commodity Carbowax of Union Carbide company ^TMAnd Polyox ^TMPolyoxyethylene glycol has for example been done introduction in its commodity bulletin F-4772-M-ICD, be incorporated herein as reference.Table 1 has been listed the Carbowax that uses among the embodiment ^TMOr Polyox ^TMPolyoxyethylene glycol product (by its molecular weight order) and their the corresponding code name given.

Table 1

Code name	ProductName and molecular weight (number average)
		??PAO-1	????Carbowax TM?PEG?400，400
??PAO-2	????Carbowax TM?PEG?1450，1450
		??PAO-3	????Carbowax TM?PEG?8000，8000
??PAO-4	????Carbowax TM?PEG?20M，20000
		??PAO-5	????Polyox TM?WSR?N-10，100000

Substantially the example of the fluoroplastic compositions of being made up of fluoroplastics and polyoxyalkylene polymers of the present invention adopts following steps to prepare.In order to make a collection of masterbatch, with Haake Rheomix 3000E mixing pressure roller with the polyoxyalkylene polymers of blend with 10% weight content melting mixing in fluoroplastics.Every batch of gross weight is 400 grams.The married operation overview be 15 rev/mins down reinforced, the time is 2 minutes, with after 1 minute, straight line rises to 50 rev/mins, keeps in addition 5 minutes again.The initial mixing temperature is 230 ℃, drops to 180 ℃ after 1 minute, keeps invariable for all the other steps.Operation is enough to obtain the final moment of torsion of constant like this, to guarantee uniform mixing.Final blend temperature is 190～210 ℃.Every batch of blend for masterbatches of gained is cut into about 0.5 inch (1.25 centimetres) cubes then all through air cooling.Again an amount of blend for masterbatches is sneaked in the fluoroplastics of equal amount with above-mentioned steps, so that in the finished product blend, finally required the polyoxyalkylene polymers of content.Before extruding, the chopping sample of finished product blend is pulverized, so that capillary rheometer is reinforced.Carry out flow measurement, be determined at the shearing stress of fluoroplastic compositions under the various shear rates, and measure because the shearing stress that exists polyoxyalkylene polymers to produce in composition descends.Use has Instron 4202 devices of 3210 capillary rheometers and measures.The kapillary die head is flat inlet, and L/D is than for about 40/1, and diameter is 20.5 mils (0.521 millimeters).Shearing stress is measured at 200 s ^-1Under carry out.Sample is extruded at 230 ℃, and the residence time is 10 minutes.Use the air cooled extrudate of microscopic examination, visual measurement extrudate appearance.

Under several constant shearing rates, extrude each fluoroplastics blend sample, reach balance until load.Table 2 is listed typical shearing rate 200s ^-1Shearing stress.Extrude each sample and finish after the measurement, with brass brush and gauze cleaning rheometer barrel, die head cleans with a wire cloth.Then, will not have the fluoroplastics of the polyoxyalkylene polymers kapillary of under constant shearing rate, flowing through, and, like this, guarantee all to remove from instrument from the polymkeric substance remnant of former extrusion until reach the predetermined apparent viscosity of unmodified fluoroplastics.

Table 2 is listed composition and the performance of one group of thermoplasticity extrudate embodiment 1-9 and comparative examples C-1.In all these embodiment, the fluoropolymer of use all is THV 500Fluoroplastic.

Table 2

Embodiment	Polyoxyalkylene polymers		Qie Yingli @200s -1	The extrudate outward appearance
							Code name	Content, % weight		Light transmission	The surface
???C-1	?-	????0	35.0 pound/inch 2(241kPa)	Transparent	Shark skin spot
						????1	?PAO-1	????0.1	31.8 pound/inch 2(219kPa)	Translucent	Shark skin spot
????2	?PAO-2	????0.1	32.1 pound/inch 2(221kPa)	Translucent	Shark skin spot
						????3	?PAO-3	????0.1	32.1 pound/inch 2(221kPa)	Translucent	Part shark skin spot
????4	?PAO-4	????0.1	33.4 pound/inch 2(230kPa)	Translucent	Shark skin spot
						????5	?PAO-5	????0.1	33.0 pound/inch 2(228kPa)	Translucent	Shark skin spot
????6	?PAO-2	????0.2	27.3 pound/inch 2(188kPa)	Translucent	Smooth
						????7	?PAO-3	????0.2	28.5 pound/inch 2(197kPa)	Translucent	Smooth
????8	?PAO-4	????0.2	30.0 pound/inch 2(207kPa)	Translucent	Smooth
						????9	?PAO-5	????0.2	31.9 pound/inch 2(220kPa)	Translucent	Part shark skin spot *

^*When PAO-5 content was 1% weight, extrudate was opaque, but smooth.

Table 2 data show, unmodified fluoro-containing plastic, and ExC-1 presents melt fracture.Along with the adding of polyoxyalkylene polymers, shearing stress reduces when extruding, if the q.s polyoxyalkylene polymers is blended in the fluoroplastics base-material, melt fracture is disappeared.

Under the condition that does not depart from the scope and spirit of the present invention, those skilled in the art obviously can carry out various replacements and change to the present invention.

Claims (13)

1. the fluoroplastic compositions of melt-processable, it comprises a kind of blend of following component:

(a) the thermoplastic fluoropolymer component of the melt-processable of more amount, but the copolymerization units of this fluoropolymer is derived from vinylidene fluoride and the undersaturated copolymerization fluorinated comonomers of at least a ethylene linkage; With

(b) the hydrocarbon polymer component containing polyoxyalkylenes of 0.01～20% weight.

2. according to the fluoroplastic compositions of claim 1, wherein said fluorinated comonomers is: (1) uses general formula R _fCF=CF ₂Expression fluoridize alpha-olefin, R in the formula _fBe H, F, Cl or the perfluoroalkyl that contains 1～8 carbon atom; With, optional (2) perfluor (alkyl vinyl ether) and/or lower molecular weight nonfluorinated alpha-olefin.

3. according to the fluoroplastic compositions of claim 1, wherein said fluoropolymer is the terpolymer of vinylidene fluoride, tetrafluoroethylene and R 1216.

4. according to the fluoroplastic compositions of claim 3, wherein said fluoropolymer contains the copolymerization units of at least 5% weight derived from 1, the 1-difluoroethylene, copolymerization units more than 25% weight is derived from the combination of tetrafluoroethylene and R 1216, and the fluorine content of fluoropolymer is up to 75% weight like this.

5. according to the fluoroplastic compositions of claim 1, wherein said fluoropolymer is the thermoplasticity terpolymer that 30～70% weight tetrafluoroethylene, 10～30% weight R 1216s and 10～50% weight vinylidene fluoride copolymerization obtain.

6. according to the fluoroplastic compositions of claim 1, wherein said fluoropolymer component ASTM D1238 melt flow index is less than 1000 Grams Per Minutes, measures under 265 ℃ and 5kg.

7. according to the fluoroplastic compositions of claim 1, the general formula of wherein said polyoxyalkylene is AC[(OR ¹), OR ²] _y, in the formula: A is the residue that does not contain active hydrogen that contains the low molecular weight initiator organic compound of a plurality of active hydrogen atoms, and y is 2 or 3, (OR ¹) _xBe the polyoxyalkylene chain that contains many oxyalkylene groups, (OR ¹), wherein said R ¹Base can be identical or different, is selected from C ₁～C ₅Alkylidene group, x are the numbers of oxyalkylene units, but described polyoxyalkylene chain homopolymer chain, or the chain of the oxyalkylene group of random distribution, or contain the alternately block or the main chain segmental chain of repeated oxidation thiazolinyl; And R ²Be selected from H, alkyl, aryl or its combination.

8. according to the fluoroplastic compositions of claim 1, wherein said polyoxyalkylene polymers is the derivative of polyoxyalkylene polyol or polyoxyalkylene polyol.

9. according to the fluoroplastic compositions of claim 1, wherein said polyoxyalkylene polymers is a polyoxyethylene glycol.

10. according to the fluoroplastic compositions of claim 9, the molecular weight ranges of wherein said polyoxyethylene glycol is about 400～20,000.

11. according to the fluoroplastic compositions of claim 1, wherein said hydrocarbon polymer component also comprises the polymkeric substance of ethene or propylene.

12. comprise the extrudate of the blend of claim 1.

13. reduce a kind of method of moulded plastic products metal defects, it comprises following component blend, (a) the thermoplastic fluoropolymer component of the melt-processable of more amount, its copolymerization units is derived from 1, but the undersaturated copolymerization fluorinated comonomers of 1-difluoroethylene and at least a ethylene linkage and (b) 0.01～20% weight comprise the hydrocarbon polymer component of polyoxyalkylene polymers; Blend melt-processed with gained is shaped to described goods again.

14. according to the method for claim 13, wherein said melt-processed comprises to be extruded.