CN1162327A - Melt-processable fluoroplastic - Google Patents
Melt-processable fluoroplastic Download PDFInfo
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- CN1162327A CN1162327A CN 95195884 CN95195884A CN1162327A CN 1162327 A CN1162327 A CN 1162327A CN 95195884 CN95195884 CN 95195884 CN 95195884 A CN95195884 A CN 95195884A CN 1162327 A CN1162327 A CN 1162327A
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Abstract
The invention provides a melt-processable fluoroplastic composition comprising a blend of a melt-processable thermoplastic fluoropolymer component of interpolymerized units derived from vinylidene fluoride and an ethylenically-unsaturated, copolymerizable, fluorinated comonomer, and a hydrocarbon polymer component comprising a polymer of ethylene or propylene. The composition is useful for making shaped articles including tubing or film.
Description
The present invention relates to thermoplastic fluoropolymer composition, its preparation and application, and relate to by for example extrude that the said composition of melt-processed prepares such as moulded products such as film and tubing.On the other hand, the present invention relates to improve the flowability of the thermoplastic fluoropolymer composition that is used to make extrusion moulding product, so that it is extruded and reduces such as metal defectses such as melt fractures under rate of extrusion fast.
The plastics of various moulding, such as film of extruding and tubing, the thermoplastic hydrocarbon polymer of melt-processable such as available polyethylene is made---referring to for example U.S. Patent No. 3,125,547 (Blatz).The environmental problem of Ti Gaoing has made people be conceived to produce many these based articles with the fluoropolymer of melt-processable day by day, and its reason is that they have relative chemical-resistant, thermostability and physical strength.For example, Canadian Patent No.958 has all described in 837 people such as () Dukert and the corresponding patent british patent specification 1,293,667 with some partial fluorine ethylene polymer and compatible poly blend and has come melt production wire insulator, film and tubing.U.S. Patent No. 4,617 has been described among 351 (Heckel, the people such as Jr.) by adding and has been improved the rate of extrusion of the thermoplasticity perfluoroparaffin polymkeric substance that some melting extrudes up to 1wt% as hydrocarbon polymers such as polyethylene.U.S. Patent No. 5,051, described a kind of thermoplastic resin composition of melt-processable among 479 (people such as Logothetis), said composition is made up of the blend of tetrafluoroethylene special elastic body polymkeric substance that is used to improve the multipolymer workability of a kind of fluorocarbon polymer (as TFE copolymer) of melt-processable and 0.05～0.5wt% basically.
The fluoropolymer that the more novel commerce of one class can obtain is the terpolymer with thermoplasticity, chemical-resistant, thermostability, optical transparence, low-permeability, it is by tetrafluoroethylene, R 1216 and vinylidene comonomer, in order to obtain different melting ranges in different ratio be combined intos.Compare with other most of fluoroplastics such as ethylene-tetrafluoroethylene copolymers with polyvinylidene difluoride (PVDF), these fluoropolymers are more soft, and can be under lower temperature melt-processed.These fluoropolymer series are sold with merchant's name of " 3M THV fluoroplastics " by 3M company, and can be used to preparation example such as moulded component and extrusion film, tubing and pattern.Because these fluoropolymers are more soft than the fluoroplastics of other melt-processable, bending easily or moulding, and have low-permeability, so they are particularly useful as the impermeable layer of automobile fuel pipeline, vapor recovery pipeline and injection or exhaust hose.Though these fluoroplastics have many good performances and processibility, but we find under some melt-processed conditions, the surface of the moulding extrudate of part fluoroplastics is undesirable coarse, demonstrate melt fracture with rough state in other words, this phenomenon is exactly well-known in the polymer melt technology " shark skin "---referring to for example " flowability of polymer melt " the 5th chapter (Brydson, J.A., Van Nostrand Reinhold Co., New York (1970)).The surface of this band defective is unsuitable for as burning line flexible pipe or (the insertion human body) conduit this class extrudate, and surface flatness is extremely important to the application of these moulded products.Especially, smooth is the requirement of conduit, flows through equably and allows lead or probe insert smoothly to guarantee liquid.Preferred smooth surface in the burning line flexible pipe is so that allow liquid laminar flow and obtain hyposmosis speed.
We find, by will be such as above-mentioned melt-processable such as 3M THV fluoroplastics, thermoplastic fluoropolymer and a spot of hydrocarbon polymer blend by vinylidene and one or more ethene unsaturated comonomer copolymerization as some alkene such as polyethylene, make the blend of acquisition can be under lower melt temperature flowability (as lower shear-stress) melt-processed to improve, rapid shaping is to have the extrudate of wishing smooth surface thus, this smooth surface can improve their usability, and these performances all are desired or requirements such as burning line flexible pipe or pipe with the character of the fluoropolymer that remains.Obtaining these improves the chemical structure do not need for example to change fluoropolymer, improves melt processing temperature or extrude under lower linear velocity and shearing rate---and these means are to adopt for reducing melt fracture in the plastic melt processing sometimes.
According to the present invention, a kind of fluoroplastic compositions of melt-processable is provided, said composition comprises (a) a kind of polymeric constituent, it accounts for the main amount (promptly being higher than 50%) of composition weight, and be the thermoplastic fluoropolymer of melt-processable, but its copolymerization units is from vinylidene and be higher than the fluorinated comonomers of the undersaturated copolymerization of ethene of 25wt%, such as (1) with general formula R
fCF=CF
2Representative fluoridize alpha-olefin, wherein R
fBe H, F, Cl or 1～8, the perfluoroalkyl of preferred 1～3 carbon atom, (2) randomly, more a spot of (promptly being lower than the 50wt% of fluoropolymer) has for example perfluor of 1～4 carbon atom (alkyl vinyl ether) [for example perfluor (methylvinylether)] and/or the low-molecular-weight alpha-olefin (for example ethene and propylene) of not fluoridizing; Fluoropolymer disperses wherein (b) a spot of (promptly being lower than the 20wt% of composition) hydrocarbon polymer component with the form of matrix, said hydrocarbon polymer component comprises the polymkeric substance of ethene or propylene, such as the homopolymer of ethene or propylene or they each other or they one of or the multipolymer of both and one or more other ethene unsaturated comonomer such as high alpha-olefins (for example 1-octene).Preferred hydrocarbon polymer component is a polyolefine, and polyethylene for example, the melt viscosity of its melt viscosity and fluoropolymer component are quite or roughly the same.The hydrocarbon polymer component is scattered in the fluoropolymer matrix equably.
On the other hand, the invention provides a kind of manufacture method of fluoroplastic compositions moulded products of melt-processable.This method comprises the thermoplastic fluoropolymer component with the melt-processable of (a) main amount, but its copolymerization units is from vinylidene and the cyaniding comonomer that is higher than the undersaturated copolymerization of ethene of 25wt%, (b) a spot of hydrocarbon polymer component blend that comprises the polymkeric substance of ethene or propylene, and blend that melt-processed obtains is shaped to goods.
When making the fluoroplastic compositions of melt-processable of the present invention, be fluorizated polymkeric substance (being referred to as " hydrocarbon ") not to be different from the fluoropolymer blend components as the hydrocarbon polymer component of blend components.
The hydrocarbon polymer component is fluid down at the melt processing temperature (for example 180～280 ℃) of fluoropolymer component, be down liquid or be preferably solid in room temperature (for example 20 ℃), and the fluoropolymer component was a solid this moment.Hydrocarbon polymer component and fluoropolymer component are immiscible, this can for example observe under the opticmicroscope, or when composition does not contain some weighting agent etc. and gives the auxiliary agent of composition color, by blend composition that extrudate produced was vaporific, white or opaque phenomenon prove.Extrudate has kept the physicals of fluoropolymer basically, such as in for example thermostability under 220～280 ℃, but compare with its extrudate, then demonstrate the melt processable or the extrusion characteristics of improvement, this is because for given extrudate shape with under higher shearing rate and the shear-stress that is even lower, the extrudate of blend composition of the present invention can be higher productive rate or faster rate extrude, extrudate has high-quality surface, particularly slipperiness does not almost have such as deleterious metal defects or melt fractures such as " shark skins " in other words.
Above-mentioned fluoropolymer preferred for the present invention is such some hydrogenous thermoplasticss, and it is 1238 that measure by ASTMD, the melt flow index under 265 ℃ and the 5kg load is lower than 1000g/min, and can melt extrudes under 250 ℃.And, the copolymerization units of the preferred 5wt% at least of fluoropolymer is from vinylidene and be higher than the mixture of the copolymerization units of 25wt% from tetrafluoroethylene and R 1216, so that the fluorine content of fluoropolymer is lower than 75wt%, and the thermoplastics extruded of melting preferably.
A class fluoropolymer preferred for the present invention is by making 30～70wt%, the tetrafluoroethylene of preferred 35～65wt%, 10～30wt%, the R 1216 of preferred 15～25wt% and 10～50wt%, the vinylidene copolymerization of preferred 15～45wt% obtains.The fluoropolymer that is used to make a group of blend of the present invention is fluoroplastics, and the copolymerization units that it contains is that the tetrafluoroethylene of 45～65wt%, the R 1216 of 10～20wt% and the vinylidene copolymerization of 20～35wt% obtain from making monomer ratio.U.S. Patent No. 4,670, such fluoroplastics of describing among 503 people such as () Newmann, its fusing point of measuring with " dsc " is 130～170 ℃, and the melt index of measuring under 265 ℃ and 5kg is 50～250g/10min.
Spendable commercial fluoropolymer is the THV fluoroplastics, the product of 3M company report 980211-7703-9 (103.02) R1,98 0211-7010-9 ,-7011-7 ,-7012-6 ,-7013-3 ,-7014-1 and-description is arranged among the 8100-7.The trade mark is the fluoroplastics of THV 200, THV 400 and THV500, the fusion range of measuring by ASTM D 3418 is respectively 115～125 ℃, 150～160 ℃ and 165～180 ℃, and the melt flow index under, 265 ℃ and the 5kg 1238 that measure by ASTM D is respectively 20,10 and 10.The description of quoting 3M THV fluoroplastics in the product report herein as a reference.
Be used for hydrocarbon olefin polymer of the present invention and can be the polymkeric substance that obtains like this, make ethene or propylene homopolymerization or make they each other they one of or both and one or more high alpha-olefins and one or more ethene unsaturated comonomer copolymerization; The content of said ethene unsaturated comonomer can be up to about 30wt%, but preferred 20wt% or lower, it can with some alkene like this, as vinyl ester compound copolymerization such as vinyl acetates.Said alkene can be used general formula CH
2=CHR represents, wherein, R is H or contains and be no more than 10 carbon atoms, the alkyl of preferred 1～6 carbon atom.Representational alkene is ethene, propylene, 1-butylene, 4-methyl-1-pentene, 1-hexene and 1-octene.Can with the representative monomers of said olefin-copolymerization vinyl ester, such as vinyl acetate, propionate, vinyl butyrate, vinyl chloroacetate and chloropropionic acid vinyl acetate; Vinyl alcohol; Vinylformic acid and alpha-alkyl vinylformic acid and alkyl ester, acid amides and nitrile are such as vinylformic acid, methacrylic acid, ethylacrylic acid, methyl acrylate, ethyl propenoate, N,N-DMAA, Methacrylamide and vinyl cyanide; Vinyl-arene is such as vinylbenzene, O-methoxy vinylbenzene, to methoxy styrene and vinyl naphthalene; The halogenide of vinyl and vinylidene is such as vinylchlorid, vinylidene chloride and inclined to one side bromine ethene; The alkyl ester of toxilic acid and fumaric acid and acid anhydrides are such as dimethyl maleate, ethyl maleate and maleic anhydride; Vinyl alkyl ethers is such as vinyl methyl ether, EVE, vinyl isobutyl ether and 2-chloroethyl vinyl ether; Vinyl pyridine; The N-vinylcarbazole; The N-vinyl pyrrolidone; And diene, such as 1,3-butadiene.The hydrocarbon olefin polymer also can be the said metal-salt that contains the olefin copolymer of free carboxylic acid groups.Can be used for providing the example of the metal of said carboxylic acid polyalcohol salt is monovalence, divalence and tervalent metal, such as sodium, lithium, potassium, calcium, magnesium, aluminium, barium, zinc, zirconium, beryllium, iron, nickel and cobalt.The representative example that is used for hydrocarbon olefin polymer of the present invention be polyethylene, polypropylene and ethene and propylene each other and/or with the multipolymer of 1-butylene, 1-hexene, 4-methyl-1-pentene or 1-octene.
The representative blend that is used for hydrocarbon olefin polymer of the present invention is the blend of polyethylene and polypropylene, new LDPE (film grade) and high density polyethylene(HDPE) and polyethylene and the olefin copolymer that contains said copolymerisable monomer etc., part in the wherein said olefin copolymer was described hereinbefore, for example, 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 hydrocarbon olefin polymer is a thermoplastic polymer, and they are multipolymers of Alathon and ethene and 1-butylene, 1-hexene, 1-octene, 4-methyl-1-pentene and propylene.
Can be used for hydrocarbon olefin polymer that commerce of the present invention can obtain and comprise Escorene available from Exxon chemical company
TMLL-3001.00, LL-5202, LD411.09 and LD760.36 polyethylene, Iotek
TM7030 iolons, and Escor
TMThe ATX310 acid ter-polymer; ER1833 polyethylene available from Chevron chemical company; Available from Novaco Chemicals, the Novapol of Inc.
TMTF 0119F polyethylene is available from the Dowlex of Dow chemical company
TM2047 polyethylene; Marlex available from Phillips 66 companies
TMHMN 4550 polyethylene; 3374X polypropylene available from Fina oiling company; And available from Miles, the Polysar of Inc.Polysar rubber branch
TMEPM 306 and EPDM 345 ethylene-propylene rubber(EPR).
Press that ASTM D 1238 measures, the melt flow index of the hydrocarbon polymer under 190 ℃ and the 2.16kg is preferably 0.01～1000, more preferably 0.1～100g/10min.Preferred hydrocarbon olefin polymer is a polyethylene.
Can be with two or more above-mentioned hydrocarbon olefin polymers as blend components (b).Perhaps be used as blend components (b) with one or more these base polymer blend and with poly-(oxyalkylene) polymkeric substance (such as polyoxyethylene glycol), each component is for example 5～95wt% of hydrocarbon blend components (b).
Be used from poly-(oxyalkylene) polymkeric substance of the present invention with hydrocarbon olefin polymer one and can comprise poly-(oxyalkylene) many alcohol and derivative thereof, they also can and be dispersed in wherein with the fluoropolymer blend.This (oxyalkylene) polymkeric substance of birdsing of the same feather flock together can be represented with following general formula:
A[(OR
1)
xOR
2]
yWherein A be low-molecular-weight, (for example have a plurality of reactive hydrogen atoms, 2 or 3) the no reactive hydrogen residue of initial organic compound, said initial organic compound is such as poly-hydroxyl alkane or polyether polyol, for example, ethylene glycol, glycerine, 1,1,1-trihydroxymethyl propane and poly-(oxypropylene) glycol; Y is 2 or 3; (OR
1)
xFor having a plurality of oxyalkylene group (OR
1) poly-(oxyalkylene) chain, wherein R
1Part can be identical or different, is selected from C
1～C
5Alkylidene group, preferred C
2Or C
3Alkylidene group; X is the number of the oxygen alkylidene unit in the said chain.Said poly-(oxyalkylene) chain can be the chain of homopolymer, and for example poly-(oxygen ethene) or poly-(oxypropylene) also can be the chain of the oxyalkylene group of random distribution (that is, mixing the embedding copolymer mixture), for example-and OC
2H
4-and-OC
3H
6-unitary multipolymer perhaps can be to have alternately block or multiple oxyalkylene group master segmental chain, for example comprises-(OC
2H
4)
a-and-(OC
3H
6)
bThe polymkeric substance of-block, a+b=5～5000 or higher wherein, for example 20,000 or higher, preferred 10～500.R
2Be H or organic group,,, also can contain O or N heteroatoms as aralkyl or alkaryl as alkyl, aryl or its combination.For example, R
2Can be that methyl, butyl, phenyl, benzyl and carboxyl groups are such as ethanoyl (CH
3CO-), benzyl acyl group (C
6H
5CO-) and stearyl-(C
17H
35CO-).
The derivative of representational poly-(oxyalkylene) polymkeric substance can comprise poly-(oxyalkylene) many alcohol derivate, and wherein terminal hydroxy group is partly or entirely changed into ether derivant (for example methoxy group) or ester derivative (stearate group (C for example
17H
35COO-)).Other useful poly-(oxyalkylene) derivatives are polyester, for example, and by the polyester of dicarboxylic acid and poly-(oxyalkylene) glycol preparation.Preferably, the derivative of poly-(oxyalkylene) polymkeric substance, the major portion of its weight should repeat oxyalkylene group (OR
1).Said poly-(oxyalkylene) many alcohol and derivative thereof can be some compounds like this, and they at room temperature are solid, and its molecular weight is at least about 200, and preferred molecular weight is about 400～20,000 or higher, for example 200,000 or higher.
Be used for poly-(oxyalkylene) many alcohol of the present invention and comprise that general formula is H (OC
2H
4)
nHow pure those of OH (wherein, n is about 15～3000) are, how pure such as what sell with the Carbowax trade mark, as Carbowax
TMPEG 8000 (wherein n is about 181), and the how alcohol of selling with the Polyox trade mark are such as Polyox
TMWSR N-10 (wherein n is about 2272).
Hydrocarbon polymer component (b) with fluoropolymer component (a) blend, the normally such amount of its content than lower bound, during by this content proportioning, compare with the identical fluoropolymer of not blend hydrocarbon polymer component (b), when improving the rate of extrusion of blend, do not observe surface imperfection in the blending extrudant as yet.Generally, the hydrocarbon polymer components contents should be about 0.01%～10wt% of fluoropolymer-hydrocarbon polymer blend, more preferably from about 0.05～5wt%, most preferably from about 0.1～1wt%.The concentration that improves hydrocarbon polymer can make the transparency of extrudate reduce usually.Some blends also can use than the more substantial special hydrocarbon polymer component (b) of other hydrocarbon polymers, so that extrudate has slick surface.Some hydrocarbon polymers contain hydrocarbon olefin polymer or the low polymkeric substance of those thermostabilitys from the polarity of polar comonomers part such as those, when being used for the colourless or transparent extrudate of requirement, may give extrudate the color that can not accept.The hydrocarbon olefin polymer that will use, its melt viscosity preferably with the melt viscosity of fluoropolymer quite or roughly the same.In order to make it consistent, can select such hydrocarbon olefin polymer, the ratio of its melt viscosity and the melt viscosity of fluoropolymer is in 0.01～10 scope, more preferably in 0.1～1 scope.In order to obtain this ratio, can under representational the same terms of melt-processed component (a) and blend (b), measure the viscosity of two kinds of polymkeric substance.By select viscosity ratio in preferable range, the hydrocarbon olefin polymer of lower aq just can make the extrudate surface obtain desirable effect, and has therefore kept the transparency of fluoropolymer significantly.
Fluoropolymer and hydrocarbon polymer component (a) and blend (b) can adopt blend means commonly used in the plastics industry to prepare, such as mixer mill, Ban Buli mixing tank or mixing forcing machine, in these mixing tanks, hydrocarbon polymer is evenly dispersed in the fluoropolymer.Fluoropolymer and hydrocarbon polymer can use with for example form of powder, particle or agglomerate.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 the form of solid granulates and be mixed, make the dried thing that mixes melt extrude machine then, hydrocarbon polymer is dispersed in the fluoropolymer matrix by twin screw.
Can or be ground into the particle diameter of hope in addition and add forcing machine (being typically single screw extrusion machine) the melt blended material pelletizing of the fluoropolymer that obtains and hydrocarbon polymer; under the temperature that depends on the fusing point of blend, melt viscosity and thermostability, for example at 180～280 ℃ of following melt-processed blends.The dissimilar forcing machine that can be used to extrude fluoroplastic compositions of the present invention for example is described in " polymer-extruded " (Rauwendaal, C., Hansen press, the 23rd～48 page, 1986).
The die orifice design of forcing machine can change with the extrudate of hope manufacturing.For example, the ring-type die orifice can be used to extrude the pipe that is used to make the burning line flexible pipe, such as U.S. Patent No. 5,284, described in 184 (people such as Noone), this description is incorporated herein by reference.
The fluoroplastics blend composition can contain additive commonly used such as oxidation inhibitor, pigment and weighting agent, for example titanium dioxide, carbon black and silicon-dioxide.
Embodiment
Following examples have been explained fluoroplastic compositions of the present invention and extrudate and advantage thereof, such as the remarkable low shear-stress that obtains when enforcement is of the present invention and the extrudate surface appearance of hope.
The fluoroplastics that are used for these embodiment are 3M THV500 fluoroplastics that commerce can obtain, and its copolymerization units is about the vinylidene of 20wt%, the tetrafluoroethylene of 60wt% and the R 1216 of 20wt% from the comonomer proportioning.The hydrocarbon polymer (being numbered PO-1, PO-2 etc.) that is used for embodiment is commercial polyolefine, and promptly with the ethene of a small amount of other olefin co-monomers, these commercial polymer products are described in the table 1.This table also comprises the ratio PO/THV500 of every kind of polyolefine and the melt viscosity of THV500 fluoroplastics under three kinds of different shear rate, and this viscosity is measured with rheology dynamic analog test instrument RDA II down at 220 ℃.Said ratio is all in the wide proportional range of hope (0.01～10), in the narrow proportional range (0.1～1) of the hope that PO-2 ,-3 ,-4 ratio are reduced to.
Table 1
| Numbering | The commercial polyethylene product trade mark | Supplier | Melting index * | Density | Comonomer | The viscosity ratio of PO/THV500 | ||
| Shearing rate s -1 | ||||||||
| ????1 | ????10 | ????100 | ||||||
| ?PO-1 | ??ER1833 | ?Chevron?Chem.Co | ??0.3 | ?0.920 | The 1-hexene | ????1.65 | ????1.19 | ????0.93 |
| ?PO-2 | ?LL-3001.00 | ?Exxon?Chem?Co. | ??1.0 | ?0.917 | The 1-hexene | ????0.60 | ????0.52 | ????0.49 |
| ?PO-3 | ???2047 | ??Dow?Chem.Co | ??2.3 | ?0.921 | The 1-octene | ????0.24 | ????0.26 | ????0.33 |
| ?PO-4 | ?HMN?4550 | ?Phillips?66?Co | ??5.0 | ?0.945 | 1-butylene | ????0.12 | ????0.14 | ????0.20 |
| ?PO-5 | ??LL-5202 | ?Exxon?Chem.Co. | ??12 | ?0.926 | 1-butylene | ????0.05 | ????0.07 | ????0.11 |
*Press that ASTM D 1238 measures, the melt index under 190 ℃, 216kg
The fluoroplastic compositions of the present invention that is used for embodiment is made up of fluoroplastics and olefin polymer basically, is to adopt the following steps preparation.In order to form a collection of masterbatch, use Haake Rheomix3000E tempering tank, the content and fluoroplastics (particle) melting mixing of the polyethylene (particle or powder) of blend being pressed 1wt%.The gross weight of every batch of material is 400g.Hybrid plan is reinforced with 2 minutes under the rotating speed of 15rpm, then brings up to 50rpm with 1 minute and keeps other 5 minutes.230 ℃ of initial mixing temperatures are reduced to 180 ℃ after 1 minute and keep constant in the step afterwards.This scheme is enough to obtain to guarantee the final moment of torsion of mixed uniformly constant.Final blending temperature is 190～210 ℃.About 0.5 cubic inch of (1.25cm is cut in the every batch of blend masterbatch air cooling that obtains then
3) particle.Then, adopt above-mentioned steps, with an amount of blend masterbatch remix in remaining fluoroplastics component, so that make the polyethylene in the finished product blend reach final hope content.The chopping sample of finished product blend is ground before extruding in advance, so that add in the capillary rheometer.Carry out ftheoloqical measurements and obtain the shear-stress of fluoroplastic compositions under various shearing rates, the reduction of shear-stress is owing to exist polyethylene in the composition.Measure with Instron4202 system and 3210 capillary rheometers.The kapillary die orifice has a L/D than the flat inlet that is about 40/l.The die orifice diameter is 23.2mil (0.589mm).Shear-stress is at 155s
-1Following mensuration.Sample is extruded after 10 minutes 220 ℃ of following pressurizes.Air cooled extrudate is estimated the surface appearance of extrudate with microscopic examination.
Each fluoroplastics blend sample is all extruded with several constant shearing rates, up to extruding equal amount.Table 2 has been listed representational constant shearing rate 155s
-1Under shear-stress.After extruding each sample and finishing mensuration, the barrel of rheometer is with copper brush and copper mesh cleaning, and die orifice is with one section metal-wire cleaning.Then, make with constant shearing rate not contain poly fluoroplastics by kapillary,, guarantee that thus the resistates of the polymkeric substance extruded previously all shifts out instrument until the apparent viscosity that reaches the unmodified fluoroplastics of measuring in advance.
Table 2 is listed the composition and the character thereof of a series of thermoplasticity extrudates of embodiment 1～10 and comparative example C-1.In all these embodiment, used fluoropolymer is all THV 500 fluoroplastics.
Table 2
| Embodiment | Polyethylene | Jian Qieyingli @155s -1 | The extrudate state | ||
| Numbering No. | Content wt% | The surface | Light transmission | ||
| ???C-1 | ????0 | ????36.2psi(250kPa) | Shark skin | Transparent | |
| ????1 | ??PO-1 | ????0.1 | ????32.3psi(223kPa) | Shark skin | Translucent |
| ????2 | ??PO-2 | ????0.1 | ????30.6psi(211kPa) | The part shark skin | Translucent |
| ????3 | ??PO-3 | ????0.1 | ????18.3psi(126kPa) | Smooth | Translucent |
| ????4 | ??PO-4 | ????0.1 | ????25.3psi(175kPa) | The part shark skin | Translucent |
| ????5 | ??PO-5 | ????0.1 | ????29.1psi(201kPa) | The part shark skin | Translucent |
| ????6 | ??PO-1 | ????1.0 | ????25.0psi(172kPa) | Smooth | White is opaque |
| ????7 | ??PO-2 | ????1.0 | ????15.8psi(109kPa) | Smooth | White is opaque |
| ????8 | ??PO-3 | ????1.0 | ????17.4psi(120kPa) | Smooth | White is opaque |
| ????9 | ??PO-4 | ????1.0 | ????17.9psi(124kPa) | Smooth | White is opaque |
| ????10 | ??PO-5 | ????1.0 | ????18.1psi(125kPa) | Smooth | White is opaque |
The data presentation of table 2 goes out, and the shear-stress of hope reduces and the more smooth extrudate surface of hope is to provide by the polyethylene blend with fluoroplastics and q.s, shown in embodiment 2～10 and correlated Embodiment C-1.Reduce though shear-stress also appears in embodiment 1, extrudate has shark skin surface (as comparative example C-1), and this is that the polyethylene of q.s just can obtain the smooth extrudate surface that (referring to embodiment 6) wishes because poly content is too low.Among the embodiment 3,,, also obtained having the smooth extrudate of hope even used the polyethylene of low amount (0.1wt%) owing to the ratio of polyethylene viscosity with fluoropolymer viscosity is reduced in the scope of wishing narrow (preferably).This data presentation goes out the relation that reduces shear-stress in polyolefinic melt viscosity and the extrusion and reduce fluoropolymer melt fracture ability.These data also demonstrate, even when other hydrocarbon olefin polymer exists with quite high content (referring to embodiment 3 and embodiment 6), the shear-stress reduction that the correct hydrocarbon olefin polymer of selecting provides equates with other hydrocarbon olefin polymer.Select best hydrocarbon olefin polymer for use, just can be with minimum use content acquisition such as improving benefit such as the transparency.
Various change of the present invention and replacement, apparent to one skilled in the art, can not depart from the scope of the present invention and spirit.
Claims (13)
1. the fluoroplastic compositions of a melt-processable comprises the blend of following component:
(a) the thermoplastic fluoropolymer component of the melt-processable of main amount, but its copolymerization units from vinylidene and be higher than 25wt% the undersaturated copolymerization of ethene fluorinated comonomers and
(b) the hydrocarbon polymer component of the polymkeric substance that comprises ethene or propylene of 0.01～20wt%.
2. the fluoroplastic compositions of claim 1, wherein said fluorinated comonomers is that (1) is with general formula R
fCF=CF
2Representative fluoridize alpha-olefin, wherein R
fBe the perfluoroalkyl of H, F, Cl or 1～8 carbon atom, and randomly, (2) perfluor (alkyl vinyl ether) and/or low-molecular-weight not fluorizated alpha-olefin.
3. the fluoroplastic compositions of claim 1, wherein said fluoropolymer is the terpolymer of vinylidene, tetrafluoroethylene and R 1216.
4. the fluoroplastic compositions of claim 3, wherein the copolymerization units of the 5wt% at least of said fluoropolymer is from vinylidene and be higher than the mixture of the copolymerization units of 25wt% from tetrafluoroethylene and R 1216, so that the fluorine content of fluoropolymer is to 75wt% nearly.
5. the fluoroplastic compositions of claim 1, wherein said fluoropolymer are the thermoplasticity terpolymers that the vinylidene copolymerization by the R 1216 of the tetrafluoroethylene of 30～70wt%, 10～30wt% and 10～50wt% forms.
6. the fluoroplastic compositions of claim 1, that wherein said fluoropolymer had was 1238 that measure by ASTM D, the melt flow index under 265 ℃ and the 5kg is lower than 1000g/min, the included polymkeric substance of wherein said hydrocarbon polymer component, it is pressed, and ASTM D 1238 measures, and the melt flow index under 190 ℃ and the 2.16kg load is 0.1～1000g/min.
7. the fluoroplastic compositions of claim 1, wherein said hydrocarbon polymer component comprises the homopolymer of ethene or propylene.
8. the fluoroplastic compositions of claim 1, wherein said hydrocarbon polymer component comprise the multipolymer of one of ethene and propylene or they or both and other ethene unsaturated comonomers.
9. the fluoroplastic compositions of claim 1, wherein said hydrocarbon polymer component comprises the multipolymer of ethene and 1-butylene, 1-hexene, 4-methyl-1-pentene or 1-octene.
10. the fluoroplastic compositions of claim 1, wherein said hydrocarbon polymer component also comprises poly-(oxyalkylene) polymkeric substance.
11. extrudate that comprises the blend of claim 1.
12. the manufacture method of a moulded plastic products, this method comprises the thermoplastic fluoropolymer component with the melt-processable of (a) main amount, but its copolymerization units is from vinylidene and the fluorinated comonomers that is higher than the undersaturated copolymerization of ethene of 25wt%, (b) the hydrocarbon polymer component blend of the polymkeric substance that comprises ethene or propylene of 0.01～20wt%, and blend that melt-processed obtains is shaped to goods.
13. the method for claim 12, wherein said melt-processed comprises to be extruded.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95195884 CN1162327A (en) | 1994-09-02 | 1995-07-25 | Melt-processable fluoroplastic |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/300,640 | 1994-09-02 | ||
| CN 95195884 CN1162327A (en) | 1994-09-02 | 1995-07-25 | Melt-processable fluoroplastic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1162327A true CN1162327A (en) | 1997-10-15 |
Family
ID=5083030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95195884 Pending CN1162327A (en) | 1994-09-02 | 1995-07-25 | Melt-processable fluoroplastic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1162327A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101715469B (en) * | 2007-06-12 | 2012-01-18 | 米利波尔公司 | Gamma ray resistant polymeric composition |
| US8658024B2 (en) | 2004-12-28 | 2014-02-25 | China Petroleum & Chemical Corporation | Catalyst and a method for cracking hydrocarbons |
-
1995
- 1995-07-25 CN CN 95195884 patent/CN1162327A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8658024B2 (en) | 2004-12-28 | 2014-02-25 | China Petroleum & Chemical Corporation | Catalyst and a method for cracking hydrocarbons |
| CN101715469B (en) * | 2007-06-12 | 2012-01-18 | 米利波尔公司 | Gamma ray resistant polymeric composition |
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