CN102112502A - Melt processible semicrystalline fluoropolymer having repeating units arising from tetrafluoroethylene, hexafluoropropylene, and hydrocarbon monomer having carboxyl group and polymerizable carbon-carbon double bond and multi-layer articles comprising same - Google Patents

Abstract

Disclosed is a melt processible semicrystalline fluoropolymer, comprising: (a) about 2 to about 20 weight percent of repeating units arising from hexafluoropropylene; (b) about 0.001 to about 1 weight percent of repeating units arising from a hydrocarbon monomer having a carboxyl group and a polymerizable carbon-carbon double bond; and (c) the remaining weight percent of repeating units arising from tetrafluoroethylene. This melt processible semicrystalline fluoropolymer is impermeable to fuels and is useful as a lining for petroleum fuel tubing, as well as chemical resistance coating for, or adhesive between, perfluoropolymer and other polymers, metals and inorganics.

Description

Have from tetrafluoroethylene, R 1216 and have carboxyl and the hemicrystalline fluoropolymer of the melt-processable of the repeating unit of the hydrocarbon monomer of polymerizable carbon-to-carbon double bond and the multi-layer product that comprises the hemicrystalline fluoropolymer layer of melt-processable

Background information

Open field

The disclosure relates generally to have the hemicrystalline fluoropolymer of melt-processable of repeating unit and the multi-layer product that comprises the hemicrystalline fluoropolymer layer of melt-processable, and described repeating unit is from tetrafluoroethylene, R 1216 and have carboxyl and the hydrocarbon monomer of polymerizable carbon-to-carbon double bond.

Association area is described

Fluoropolymer is important commerical prod because of their low surface energy and high heat-resisting forming with chemical-resistant.Yet their low surface energy causes the poor adhesion to substrate usually.

Known some functional group can change the bond properties of partially fluorinated polymkeric substance.Up to the present, during the polyreaction of partially fluorinated polymkeric substance, sneak into this type of group and significantly do not reduce required polymer performance, obtained limited success.The monomer that comprises functional group may be not and the fluorinated monomer copolymerization, or may cause other worthless effect during copolyreaction.In addition, incorporate thermostability or the chemical-resistant that the monomer that comprises functional group may influence resulting polymers unfriendly into.

The fluoropolymer that therefore, need also have the thermally-stabilised and chemicals-resistant of bond properties.

Can on metal base, form partially fluorinated polymeric coating by known method, wherein make metallic surface roughen and primer coating, then the coating deposition partially fluorinated polymer beads of fused then thereon.This complicacy and the cost that makes metal roughen and use priming paint increase industrial process.

Therefore, need heat-resisting and fluoropolymer chemicals-resistant also to have bond properties, and need not priming paint or make the metallic surface roughen metal.

A business method relates to surface treatment, Corona discharge Treatment or the plasma discharge treatment that makes the fluoropolymer property management stand chemical reagent, applies with tackiness agent usually then.Then nonfluorinated polymers such as polymeric amide are expressed on the outside surface of fluoropolymer property management of modification like this.This adhesive bonding method has increased the complicacy of this industrial process and cost and has reduced the output of this industrial process.

Therefore, need need not this surface treated fluoropolymer, and wherein might form multi-layer product with nonfluorinated polymers by method for melt processing such as coextrusion under rational processing temperature.

Multi-layer product with non-fluorinated polymer layer and fluorinated polymer layer is benefited from characteristic such as the thermotolerance and the chemical substance impenetrability of fluorinated polymer, and benefit from the characteristic of nonfluorinated polymers such as high strength, high tenacity, in light weight, processibility good, pliable and tough and can afford.Find that the multi-layer product with fluorinated polymer layer and aramid layer can be used for supply of fuel in the device by the oil engine energy supply.In this based article, need contiguous fluorinated polymer layer and aramid layer bonded to each other.

Yet the multi-layer product with non-fluorinated polymer layer and fluorinated polymer layer generally is subjected to the low puzzlement of interfacial adhesion, and this may cause layering and structural failure in use.

Carried out attempting trying hard to strengthen the interlayer adhesion of this based article by blend.Under expectation fluorinated polymer and polymeric amide adherent situation, disclose as the polymeric amide of tackiness agent and the blend of fluorinated polymer.Yet in the method, the form of tackiness agent changes according to molded condition, and this is because the intrinsic consistency between the component resin is poor in the blend.The change of form also influences the bond strength of binder layer self unfriendly, with and with the binding property of other layer.In addition, this technology can not improve the binding property of fluorinated polymer self and only be the binding property of utilizing blend.The use of this type of polymer blend causes damage to desired fluorinated polymer characteristic.

Carried out attempting trying hard to by the fluorinated polymer modification being strengthened the interlaminar adhesion of this based article.Under expectation fluorinated polymer and polymeric amide adherent situation, by for example grafting or copolymerization with the fluorinated polymer modification to comprise anhydride group.Yet in these methods, the fluorinated polymer of modification is subjected to the puzzlement of multiple shortcoming, for example, lacks melt-processible under the required temperature of melt-processed polymeric amide; Do not have crystalline melt point and have amorphous and the rubber elastomer characteristics that is not suitable for melt processing such as coextrusion; Or the fluorinated polymer of modification comprises relatively large anhydride group, and is subjected to the puzzlement that thermolability and chemical substance impenetrability reduce.

Therefore, need have the multi-layer product of non-fluorinated polymer layer and fluorinated polymer layer, wherein: (1) nonfluorinated polymers and fluorinated polymer be strong binding each other; (2) goods are easy to make by the method for melt processing such as the coextrusion of routine; And (3) goods have fluorinated polymer characteristic such as thermotolerance and chemical substance impenetrability, and have nonfluorinated polymers characteristic such as high strength, high tenacity, in light weight, processibility good, pliable and tough and can afford.

Summary of the invention

This paper has described the hemicrystalline fluoropolymer of melt-processable, described fluoropolymer because of with multiple substrate strong binding, because of reasonably using the ordinary method melt-processed under the processing temperature, and because of having thermotolerance and the chemical-resistant that can be used in the commercial applications scope, and satisfied industrial requirements.

This paper has described the hemicrystalline fluoropolymer of melt-processable, and described fluoropolymer comprises: (a) about 2 weight % to about 20 weight % from the R 1216 repeating unit of (also being called as HFP herein); (b) about 0.001 weight % to about 1 weight % from the repeating unit of (also being called as monomer or FG herein) of the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond; (c) all the other weight percents from the tetrafluoroethylene repeating unit of (also being called as TFE herein).

Above only property and illustrative purpose presented for purpose of illustration of summary and following detailed Description Of The Invention, rather than limit the invention, the present invention is limited by the appended claims.

The accompanying drawing summary

Embodiment has been shown to strengthen in the accompanying drawing to the understanding of existing notion herein.

Fig. 1 shows the sectional view with two-layer multi-layer product of the present invention.

Fig. 2 shows the sectional view with trilaminar multi-layer product of the present invention.

Fig. 3 shows the sectional view with two-layer multilayered tube of the present invention.

Fig. 4 shows the sectional view with trilaminar multilayered tube of the present invention.

The technician understands, and the object in the accompanying drawing is with shown in the short and sweet mode, and not drawn on scale.For helping to understand, the size of some layer among the figure has been amplified with respect to other layer.

Although will describe the present invention, be to be understood that it is not intended to limit the invention to this embodiment in conjunction with its preferred embodiment.On the contrary, it is intended to contain all replacement schemes, modification and equivalent in the spirit and scope of the invention that may be included in the appended claims qualification.

Detailed Description Of The Invention

In an embodiment of the hemicrystalline fluoropolymer of melt-processable, the hemicrystalline fluoropolymer of described melt-processable comprises: (a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %; (b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %; (c) about 0.5 weight % is to the repeating unit from perfluor (alkyl vinyl ether) of about 10 weight %; (d) repeating unit from tetrafluoroethylene of all the other weight percents; Wherein from the repeating unit weight percent of R 1216 with from the repeating unit weight percent sum of perfluor (alkyl vinyl ether) greater than about 4 weight % and less than about 20 weight %.

In another embodiment, the hemicrystalline fluoropolymer of described melt-processable comprises: (a) about 4 weight % are to the repeating unit from R 1216 of about 14 weight %; (b) about 0.001 weight % to about 1 weight % from having carboxyl and polymerizable carbon-to-carbon double bond and comprising the di-carboxylic acid anhydride group or the repeating unit of the hydrocarbon monomer of di-carboxylic acid group; (c) about 0.5 weight % is to the repeating unit from perfluor (alkyl vinyl ether) of about 3 weight %; (d) repeating unit from tetrafluoroethylene of all the other weight percents.

In another embodiment, this paper has described the mixture of melt blending, described mixture comprises the hemicrystalline fluoropolymer of polymkeric substance and melt-processable, and the hemicrystalline fluoropolymer of wherein said melt-processable comprises: (a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %; (b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %; (c) repeating unit from tetrafluoroethylene of all the other weight percents.

In another embodiment, this paper has described multi-layer product, described goods have the layer of the hemicrystalline fluoropolymer that comprises melt-processable, and the hemicrystalline fluoropolymer of wherein said melt-processable comprises: (a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %; (b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %; (c) repeating unit from tetrafluoroethylene of all the other weight percents.

In another embodiment, this paper has described multi-layer product, and described goods comprise: (A) comprise the first layer of at least a material, described material is selected from nonfluorinated polymers, metal and the inorganics with polar functional group; (B) comprise the second layer of the hemicrystalline fluoropolymer of melt-processable, the hemicrystalline fluoropolymer of wherein said melt-processable comprises: (a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %; (b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %; (c) repeating unit from tetrafluoroethylene of all the other weight percents, wherein (A) and (B) adjacency.

Above-mentioned embodiment only is exemplary rather than restrictive.After running through this specification sheets, the technician it should be understood that without departing from the present invention other aspects and embodiment also are possible.

By reading following detailed Description Of The Invention and claim, the further feature and the beneficial effect of any one or a plurality of embodiments will become apparent.Detailed Description Of The Invention has at first been discussed the definition of 1. terms and has been illustrated, and has then discussed: 2. perfluorinated monomers; 3. monomer (FG); 4.FG-fluoropolymer fusing point and melt flow rate (MFR); 5.FG-fluoropolymer fluorine content; 6.FG-fluoropolymer fuel vapours transfer rate; 7. the FG-fluoropolymer that comprises perfluorinated monomers and FG; 8. the FG-fluoropolymer that comprises TFE, HFP and FG; 9. the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG; 10. optional monomers; 11. prepare the method for FG-fluoropolymer; 12.FG-fluoropolymer purposes; 13. multi-layer product; 14. multi-layer product the first layer (A)-the have nonfluorinated polymers of polar functional group; 15. multi-layer product the first layer (A)-the have thermoplastics of amine functional group; 16. multi-layer product the first layer (A)-metal; 17. multi-layer product the first layer (A)-inorganics; 18. multi-layer product is chosen the 3rd layer of (B1)-(per) fluoropolymer wantonly; 19. the thickness of multi-layer product layer; 20. prepare the method for multi-layer product; And embodiment.

1. the definition of term and illustrating

Before proposing following embodiment details, define or illustrate some terms earlier.

The hemicrystalline hemicrystalline fluoropolymer of melt-processable that is meant has certain degree of crystallinity, and is feature with the fusing point measured that records according to ASTM D 4501 with at least about the fusion heat absorption of 3J/g.Hemicrystalline fluoropolymer is different from the amorphous fluoropolymer.

Melt-processable is meant that polymkeric substance can use conventional plastic processing technology such as melt extrusion to process.

The hemicrystalline fluoropolymer of melt-processable as herein described also is called as " FG-fluoropolymer " in this article, and described fluoropolymer comprises the repeating unit from R 1216 of (a) about 2 weight % to about 20 weight %; (b) about 0.001 weight % to about 1 weight % from the repeating unit of hydrocarbon monomer and (c) repeating unit from tetrafluoroethylene of all the other weight percents with carboxyl and polymerizable carbon-to-carbon double bond.

As used herein, term " comprises ", " comprising ", " having " or their any other modification all are intended to contain comprising of nonexcludability.For example, comprise that technology, method, goods or the equipment of key element tabulation needn't only limit to those key elements, but can comprise clearly do not list or this technology, method, goods or equipment institute other key elements of inherent.In addition, unless opposite offering some clarification on arranged, " or " be meant inclusive " or ", rather than refer to exclusiveness " or ".For example, below all satisfy condition A or B:A of any situation be that real (or existence) and B are false (or non-existent), A is that false (or non-existent) and B are real (or existence), and A and B are real (or existence).

Equally, use " one " or " a kind of " to describe key element described herein and component.Doing so only is for convenience, and provides general meaning to scope of the present invention.This description should be understood to include one or at least one, and this odd number also comprises plural number, anticipates unless clearly refer to him in addition.

Unless otherwise defined, otherwise all technology used herein have the common identical meaning of understanding with the claim those of ordinary skill in the field with scientific terminology.Although also can be used for hereinafter having described suitable method and material in the enforcement or test of disclosed embodiment with method as herein described and materials similar or the method that is equal to and material.Remove the non-quoted physical segment and fall, otherwise all publications that this paper mentions, patent application, patent and other reference all in full way of reference incorporate this paper into.As conflict, the definition included with this specification sheets is as the criterion.In addition, material, method and embodiment only are exemplary, are not intended to limit.

For the content that this paper does not describe, the many details that relate to concrete material and treatment process are conventional, and can find in the textbook of polymer arts and other resource.

2. perfluorinated monomers

Perfluorinated monomers is defined as the compound of containing element carbon and fluorine and carbon-to-carbon degree of unsaturation herein.The monovalent atom of all and bond with carbon all is fluorine in the perfluorinated monomers.In one embodiment, perfluorinated monomers also comprises at least one heteroatoms, and described heteroatoms is selected from oxygen, sulphur and nitrogen.

In one embodiment, the available perfluorinated monomers comprises perfluoroolefine and the perfluorinated vinyl ethers with 2 to 8 carbon atoms.In another embodiment, perfluorinated vinyl ethers is by formula CF ₂=CFOR or CF ₂=CFOR ' OR represents that wherein R is the perfluorination straight or branched alkyl that comprises 1 to 5 carbon atom, and R ' is for comprising the perfluorination straight or branched alkylidene group of 1 to 5 carbon atom.In another embodiment, the R group comprises 1 to 4 carbon atom.In another embodiment, R ' group comprises 2 to 4 carbon atoms.

The perfluorinated monomers example comprises tetrafluoroethylene (TFE), R 1216 (HFP), perfluor-2,2-dimethyl-1,3-dioxole (PDD), perfluor-2-methylene radical-4-methyl isophthalic acid, 3-dioxolane (PMD), perfluor-3,6-two oxa-s-4-methyl-7-octene sulfonic acid fluoride (PSEPVE) and perfluor (alkyl vinyl ether) (PAVE), as perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) (PEVE), perfluor (propyl vinyl ether) (PPVE) and perfluor (butyl vinyl ether) (PBVE).

In one embodiment, the hemicrystalline fluoropolymer of melt-processable comprises the repeating unit from perfluorinated monomers and monomer, and except the repeating unit from the monomer, is fluoridized.

3. monomer (FG)

Monomer (FG) comprises carboxyl (C (=O) O-) and polymerisable carbon-to-carbon double bond.FG does not comprise fluorine.

In one embodiment, FG comprises di-carboxylic acid anhydride group (C (=O) OC (=O)-) and polymerisable double bonds.

In another embodiment, FG comprises di-carboxylic acid group and polymerisable double bonds.In another embodiment, FG comprises 1,2-or 1,3-di-carboxylic acid group and polymerisable carbon-to-carbon double bond.

In another embodiment, FG comprises the C that comprises the polymerizable carbon-to-carbon double bond ₄To C ₁₀Di-carboxylic acid and dicarboxylic acid anhydride.For example: maleic anhydride, dichloromaleic anhydride, toxilic acid, fumaric acid, itaconic anhydride, methylene-succinic acid, citraconic anhydride, citraconic acid, methylfumaric acid, 5-norborneol-2,3-dicarboxylic anhydride and 5-norborneol-2,3-dicarboxylic acid.

In one embodiment, the FG-fluoropolymer comprises the repeating unit from FG of about 0.001 weight % to about 1 weight %.In another embodiment, the FG-fluoropolymer comprises the repeating unit from FG of about 0.001 weight % to about 0.5 weight %.In another embodiment, the FG-fluoropolymer comprises the repeating unit from FG of about 0.001 weight % to about 0.3 weight %.In another embodiment, the FG-fluoropolymer comprises the repeating unit from FG of about 0.001 weight % to about 0.1 weight %.In another embodiment, the FG-fluoropolymer comprises the repeating unit from FG of about 0.001 weight % to about 0.01 weight %.

4.FG-fluoropolymer fusing point and melt flow rate (MFR)

FG-fluoropolymer fusing point can be measured according to ASTM method D 4591-01 " Standard Test Method for Determining Temperatures and Heats of Transitions of Fluoropolymers by Differential Scanning Calorimetry ".

In one embodiment, FG-fluoropolymer fusing point is lower than about 265 ℃.In another embodiment, FG-fluoropolymer fusing point is lower than about 260 ℃.In another embodiment, FG-fluoropolymer fusing point is lower than about 250 ℃.In another embodiment, FG-fluoropolymer fusing point is lower than about 240 ℃.In another embodiment, FG-fluoropolymer fusing point is lower than about 230 ℃.In another embodiment, FG-fluoropolymer fusing point is lower than about 225 ℃.In another embodiment, FG-fluoropolymer fusing point is lower than about 220 ℃.

FG-fluoropolymer melt flow rate (MFR) can be measured according to ASTM method D1238-04c.FG-fluoropolymer MFR can be appointed as the value with specific end use, and for example the MFR of the another kind of polymkeric substance of coextrusion is similar with it to described FG-fluoropolymer.

In one embodiment, the MFR of FG-fluoropolymer is about 1 to about 400g/10min.In another embodiment, the MFR of FG-fluoropolymer is about 10 to about 300g/10min.In another embodiment, the MFR of FG-fluoropolymer is about 1 to about 100g/10min.In another embodiment, the MFR of FG-fluoropolymer is about 20 to about 90g/10min.In another embodiment, the MFR of FG-fluoropolymer is about 1 to about 50g/10min.In another embodiment, the MFR of FG-fluoropolymer is about 5 to about 40g/10min.In another embodiment, the MFR of FG-fluoropolymer is about 10 to about 30g/10min.In another embodiment, the MFR of FG-fluoropolymer is about 15 to about 30g/10min.In another embodiment, the MFR of FG-fluoropolymer is about 20 to about 30g/10min.

5.FG-the fluorine content of fluoropolymer

The fluorine content of FG-fluoropolymer can be determined by mass balance according to the used up amount of monomer of polymerization process that is used for preparing the FG-fluoropolymer.In one embodiment, the fluorine content of FG-fluoropolymer is at least about 65 weight %.In another embodiment, the fluorine content of FG-fluoropolymer is at least about 70 weight %.In another embodiment, the fluorine content of FG-fluoropolymer is at least about 75 weight %.

6.FG-fluoropolymer fuel vapours transfer rate

The FG-fluoropolymer has resistance to the infiltration of liquid fuel and liquid petroleum product such as gasoline, CE10 (mixture of 10 volume % ethanol and surplus gasoline (10 weight % ethanol, 45 weight % octane-iso, 45 weight % toluene)), CE85 (mixture of 85 volume % ethanol and surplus gasoline), diesel oil, domestic fuel oil, biofuel and biofuel.The FG-fluoropolymer also has resistance to industrial solvent as the infiltration of alcohol, ketone and ester.

In one embodiment, recorded by method described in the SAE J2659-03,40 ℃ of following CE10 fuel vapours transfer rates are not more than about 0.1gmm/m ²D.In another embodiment, recorded by method described in the SAEJ2659-03,40 ℃ of following CE10 fuel vapours transfer rates are not more than about 0.05gmm/m ²D.In another embodiment, recorded by method described in the SAE J2659-03,40 ℃ of following CE10 fuel vapours transfer rates are not more than about 0.04gmm/m ²D.

7. the FG-fluoropolymer that comprises perfluorinated monomers and FG

In one embodiment, the hemicrystalline fluoropolymer of melt-processable comprises repeating unit, and described repeating unit is from (a) perfluorinated monomers; (b) about 0.001 weight % is to the FG of about 1 weight %; The hemicrystalline fluoropolymer of wherein said melt-processable has and is lower than about 265 ℃ fusing point and at least about the fluorine content of 69 weight %.

8. the FG-fluoropolymer that comprises TFE, HFP and FG

In one embodiment, the hemicrystalline fluoropolymer of melt-processable comprises: (a) about 2 weight % are to the repeating unit from HFP of about 20 weight %; (b) about 0.001 weight % is to the repeating unit from FG of about 1 weight %; (c) repeating unit from TFE of all the other weight percents.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP and FG comprises the repeating unit from HFP of about 4 weight % to about 20 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP and FG comprises the repeating unit from HFP of about 4 weight % to about 14 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP and FG comprises the repeating unit from HFP of about 8 weight % to about 12 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP and FG comprises the repeating unit from HFP of about 10 weight % to about 12 weight %.

Imagined in the FG-fluoropolymer that comprises TFE, HFP and FG various embodiments, and above be described among part 3. monomers (FG) from the repeating unit amount of FG.

9. the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG

In one embodiment, the hemicrystalline fluoropolymer of melt-processable also comprises from perfluor (alkyl vinyl ether) repeating unit (PAVE).

In another embodiment, the hemicrystalline fluoropolymer of melt-processable comprises: (a) about 2 weight % are to the repeating unit from HFP of about 20 weight %; (b) about 0.001 weight % is to the repeating unit from FG of about 1 weight %; (c) about 0.5 weight % is to the repeating unit from PAVE of about 10 weight %; (d) repeating unit from TFE of all the other weight percents; Wherein from the repeating unit weight percent of HFP with from the repeating unit weight percent sum of PAVE greater than about 4 weight % and less than about 20 weight %.

In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises the repeating unit from HFP of about 4 weight % to about 20 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises the repeating unit from HFP of about 4 weight % to about 16 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises the repeating unit from HFP of about 8 weight % to about 16 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises the repeating unit from HFP of about 9 weight % to about 14 weight %.

In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises the repeating unit from PAVE of about 0.5 weight % to about 3 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises the repeating unit from PAVE of about 1 weight % to about 10 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises the repeating unit from PAVE of about 2 weight % to about 8 weight %.In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises the repeating unit from PAVE of about 3 weight % to about 7 weight %.

Imagined in the hemicrystalline fluoropolymer of TFE/HFP/PAVE/FG melt-processable various embodiments, and above be described among part 3. monomers (FG) from the repeating unit amount of FG.

In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises: (a) repeating unit from HFP of about 12 weight %; (b) about 0.01 weight % is to the repeating unit from FG of about 0.1 weight %; (c) the repeating unit of about 0.75 weight % from PAVE; (d) repeating unit from TFE of all the other weight percents.

In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises: (a) repeating unit from HFP of about 12 weight %; (b) about 0.01 weight % is to the repeating unit from FG of about 0.1 weight %; (c) the repeating unit of about 1.5 weight % from PAVE; (d) repeating unit from TFE of all the other weight percents.

In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises: (a) repeating unit from HFP of about 6 weight %; (b) about 0.01 weight % is to the repeating unit from FG of about 0.1 weight %; (c) the repeating unit of about 2 weight % from PAVE; (d) repeating unit from TFE of all the other weight percents.

In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises: (a) repeating unit from HFP of about 5 weight %; (b) about 0.01 weight % is to the repeating unit from FG of about 0.1 weight %; (c) the repeating unit of about 5 weight % from PAVE; (d) repeating unit from TFE of all the other weight percents.

In another embodiment, the FG-fluoropolymer that comprises TFE, HFP, PAVE and FG comprises: (a) about 5 weight % are to the repeating unit from HFP of about 6 weight %; (b) about 0.01 weight % is to the repeating unit from FG of about 0.1 weight %; (c) about 6 weight % are to the repeating unit from perfluor (methylvinylether) of about 7 weight %; (d) about 86 weight % are to the repeating unit from TFE of about 89 weight %.

10. Ren Xuan monomer

In one embodiment, the optional repeating unit that comprises from non-perfluorinated monomer of FG-fluoropolymer, described non-perfluorinated monomer such as ethene, propylene, vinylidene fluoride, vinyl fluoride, chlorotrifluoroethylene and perfluor-4,7-two oxa-s-5-methyl-8-methyl pelargonate (EVE).If the repeating unit from this type of non-perfluorinated monomer is contained in the FG-fluoropolymer, then they are not to reduce FG-fluoropolymer fuel infiltration resistance and/or the existence of the low levels of other useful (for example binding property) characteristic.

In one embodiment, the FG-fluoropolymer also comprise about 0.1 weight % to about 5 weight % from the repeating unit that is not the non-perfluorinated monomer of FG.

In one embodiment, the FG-fluoropolymer also comprises about 1 weight % or lower from the repeating unit that is not the non-perfluorinated monomer of FG.

11. prepare the method for FG-fluoropolymer

In one embodiment, can be by as United States Patent (USP) 6,107, in 423 disclosed in supercritical co the polymeric currently known methods, preparation FG-fluoropolymer.

In another embodiment, can be by the aqueous dispersion polymerisation process described in the embodiment of the invention 2 and 3, preparation FG-fluoropolymer.

12.FG-the purposes of fluoropolymer

The FG-fluoropolymer has as tackiness agent with the purposes of bonding (per) fluoropolymer (for example PTFE, FEP, PFA) with polymkeric substance, metal or inorganics substrate.(per) fluoropolymer and FG-fluoropolymer strong binding, and FG-fluoropolymer and many polymkeric substance, metal and inorganics strong binding.

In one embodiment, the FG-fluoropolymer can be used in the adhesive article (per) fluoropolymer with have the thermoplastics of amine functional group, described goods are as the polymeric amide pipe of the (per) fluoropolymer liner that can be used for the oil fuel supply.In order to form this based article, the FG-fluoropolymer layer is melt extruded as the interlayer that (per) fluoropolymer melt extrudes between layer and the molten polyamide extruding layer.

In one embodiment, substrate comprises and FG-fluoropolymer carboxyl reaction, or in other words with the powerful associating functional group (for example amine) of FG-fluoropolymer carboxyl, between FG-fluoropolymer and this type of substrate, produce strong adhesive power.

In another embodiment, the FG-fluoropolymer aqueous dispersion can with another kind of aqueous polymer dispersion blend, then the polymer dispersion of blend is separated, and as tackiness agent for example.In another embodiment, the FG-fluoropolymer can with another kind of polymer melt blend, and the gained melt blended material is as tackiness agent for example.This paper comprises the composition that comprises melt-blended mixtures, and described melt-blended mixtures comprises FG-fluoropolymer and another kind of polymkeric substance.

In another embodiment, make the FG-fluoropolymer treat that as two kinds the binder layer between other polymer layer of adherent comes coextrusion.

Can realize the purposes of FG-fluoropolymer, realize known to other type polymer of identical purpose using similar approach as this area as tackiness agent.For example, the equipment of known use such as screw extrusion press comes the melting mixing polymkeric substance.Similarly, comprise that it also is known that the multilayer film that uses binder layer or knitting layer is extruded.

13. multi-layer product

This paper comprises multi-layer product, and described preparation has the layer that comprises the FG-fluoropolymer.In one embodiment, multi-layer product is a layered product, and described layered product comprises the material that a slice is made by at least two different bonding coats.In another embodiment, multi-layer product comprises: (A) comprise the first layer of at least a material, described material is selected from nonfluorinated polymers, metal and the inorganics with polar functional group; (B) comprise the second layer of FG-fluoropolymer, wherein (A) and (B) adjacency.

In one embodiment, multi-layer product is a multilayered tube, and described multilayered tube has at least one layer that comprises the FG-fluoropolymer.In another embodiment, multi-layer product is an insulated line, and described insulated line has at least one layer that comprises the FG-fluoropolymer.In another embodiment, multi-layer product is the melt extrusion die head, and described die head has the flow passage that applies the FG-fluoropolymer.In another embodiment, multi-layer product is an electron device, and described electron device has at least one layer that comprises the FG-fluoropolymer.In another embodiment, multi-layer product is an optical fiber, and described optical fiber has at least one layer that comprises the FG-fluoropolymer.

Fig. 1 shows the sectional view of one embodiment of the invention, described embodiment is to have two-layer multi-layer product, described goods comprise: (A) comprise the first layer of at least a material, described material is selected from nonfluorinated polymers, metal and the inorganics with polar functional group; (B) comprise the second layer of FG-fluoropolymer.The one side adjacency of the one side of the second layer (B) and the first layer (A).

Fig. 2 shows the sectional view of one embodiment of the invention, described embodiment is for having trilaminar multi-layer product, described goods comprise: (A) comprise the first layer of at least a material, described material is selected from nonfluorinated polymers, metal and the inorganics with polar functional group; (B) comprise the second layer of FG-fluoropolymer; (B1) comprise the 3rd layer of (per) fluoropolymer.First adjacency of the one side of the 3rd layer (B1) and the second layer (B), and second adjacency of the one side of the first layer (A) and the second layer (B), described second with the second layer (B) first is relative.

Fig. 3 shows the sectional view of one embodiment of the invention, and described embodiment is to have two-layer multilayered tube, and described multilayered tube comprises: the first layer (A) that comprises the nonfluorinated polymers with polar functional group; With the second layer that comprises the FG-fluoropolymer (B); Wherein said layer arranged in co-axial alignment makes the first layer (A) in the second layer (B) outside.The inner face adjacency of the outside of the second layer (B) and the first layer (A).

Fig. 4 shows the sectional view of one embodiment of the invention, and described embodiment is for having trilaminar multilayered tube, and described multilayered tube comprises: the first layer (A) that comprises the nonfluorinated polymers with polar functional group; The second layer (B) that comprises the FG-fluoropolymer; With the 3rd layer (B1) comprising (per) fluoropolymer; Wherein said layer arranged in co-axial alignment make the second layer (B) in the 3rd layer (B1) outside, and the first layer (A) is in the second layer (B) outside.The inner face adjacency of the outside of the 3rd layer (B1) and the second layer (B), and the inner face adjacency of the outside of the second layer (B) and the first layer (A).

14. multi-layer product the first layer (A)-the have nonfluorinated polymers of polar functional group

In one embodiment, the first layer (A) comprises the nonfluorinated polymers with polar functional group.Described polar functional group is at least a following functional group that is selected from: amine, acid amides, imide, nitrile, carbamate, chlorine root, ether, ester, hydroxyl, carbonate and carboxyl.Nonfluorinated polymers example with polar functional group is at least a following material: the EEA (ethylene-propylene acetoacetic ester) that is selected from, EMA (ethylene-methyl acrylate), EVOH (polythene-ethenol multipolymer), PA (polymeric amide), PET (polyethylene terephthalate), PI (polyimide), PMMA (polymethylmethacrylate), PVA (polyvinyl acetate), PVAL (polyvinyl alcohol), polycarbonate (PC), polyvinyl butyral acetal (PVB), urethane (PU), polyacrylonitrile (PAN) and PVC (polyvinyl chloride).

15. multi-layer product the first layer (A)-the have thermoplastics of amine functional group

In one embodiment, the first layer (A) nonfluorinated polymers comprises the thermoplastics with amine functional group.The thermoplastics that available has amine functional group has: (i) about 50 or the lower relative viscosity (rV) that is recorded by ASTM D789; (ii) about 10meq or bigger, preferred 20meq or the bigger every kg of amine end groups have the thermoplastics of amine functional group.Amine end groups such as MelvinL.Kohan in " Nylon Plastics Handbook " definition, and can be by currently known methods as by measuring with perchloric acid titration.

Thermoplastics example with amine functional group comprises at least a following material that is selected from: polymeric amide, poly-(ethyliminum) (PEI), polyallylamine, polyvinylamine, polyvinylpyridine, diallyl dimethyl ammoniumchloride and as U.S. Pat 5,128, disclosed polyformaldehyde composition in 405, described composition comprises the amine polymer with side group amine functional group.

Representational polyamide thermoplastic is that melting is extruded, and generally has the number-average molecular weight at least about 5,000.The polymeric amide example comprise by equimolar amount at least a comprise the saturated dicarboxylic acid of 4 to 14 carbon atoms and at least a condensation reaction that comprises the diamines of 4 to 14 carbon atoms makes those.Yet, can use excessive diamines that amido end group above carboxyl end groups in the polymeric amide is provided.Specific examples comprises polyhexamethylene adipamide (nylon 66), poly-azelaoyl hexanediamine (nylon 69), polyhexamethylene sebacamide (NYLON610), nylon 612 (nylon 612) and polycaprolactam (nylon 6).The aromatic polyamide that melting is extruded (for example aliphatic series-aromatic polyamide, with respect to aromatic poly) is an available.The example of this type of semiaromatic polyamide composition comprises Amodel

The multipolymer of A1000 and paraphenylene terephthalamide's 2 methyl pentamethylenediamine and hexamethylene terephthalamide such as Zytel

HTN 501 is (by E.I.du Pont de Nemours﹠amp; Co. (Wilmington DE) produces).The elastomer-modified type of this type of aliphatic series and aromatic polyamide also is available, for example Amodel

ET1000HSNT (Amoco).Polymeric amide is a polymkeric substance well known in the art.Referring to the 454th page (1996) of the 4th edition the 19th volume of for example Kirk-Othmer " Encyclopedia of Chemical Technology ".

16. multi-layer product the first layer (A)-metal

In one embodiment, the first layer (A) comprises at least a material that is selected from periodic table of elements IB, IIB, IIIB, IVB, VB, VIB, VIIB, VIIIB, IIIA and IVA family metal.These metals comprise lithium, beryllium, sodium, magnesium, aluminium, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, caesium, barium, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead and bismuth.In one embodiment of the invention, described metal is at least a following metal that is selected from: aluminium, chromium, cobalt, copper, iron, manganese, molybdenum, nickel, niobium, rhenium, steel, tantalum, titanium, tungsten and zirconium.In another embodiment, described metal comprises above-mentioned mixture, comprises for example Inconel of alloy

And Hastelloy

In another embodiment, described metal also comprises nonmetal.An example of this embodiment is the steel that comprises iron and carbon.

17. multi-layer product the first layer (A)-inorganics

In one embodiment, the first layer (A) comprises inorganics.Inorganics or inorganic substance are meant and do not comprise the material of carbon as principal element except carbonate, Wimet, prussiate and cyanates.The inorganic substance example is synthetic compound and natural mineral and rock, comprises silicate, carbonate, vitriol, halogenide, oxide compound or sulfide.The inorganic substance example comprises glass, perlite, gypsum, vermiculite, zeolite, pottery, clay, cement, concrete, mortar, stone material, fragment of brick, silicon-dioxide, phosphoric acid salt, alumina, sodium-chlor and lime carbonate.

18. multi-layer product is chosen the 3rd layer of (B1)-(per) fluoropolymer wantonly

The available (per) fluoropolymer is that melting is extruded.In one embodiment, as measured to concrete (per) fluoropolymer usually, (per) fluoropolymer has 0.5 * 10 ³To 60 * 10 ³Melt viscosity in the Pas scope.By currently known methods, the polyreaction by at least a perfluorinated monomers makes (per) fluoropolymer.(per) fluoropolymer comprises the multipolymer of tetrafluoroethylene (TFE) and one or more polymerizable perfluorinated comonomer, described polymerizable perfluorinated comonomer is as perfluoroolefine (for example R 1216 (HFP)) with 3 to 8 carbon atoms and/or perfluor (alkyl vinyl ether) (PAVE), wherein said perfluoroalkyl comprises 1 to 5 carbon atom, and is straight or branched.Available PAVE monomer can be by formula CF ₂=CFOR or CF ₂=CFOR ' OR represents that wherein R is the perfluorination straight or branched alkyl with 1 to 5 carbon atom, and R ' is for having the perfluorination straight or branched alkylidene group of 1 to 5 carbon atom.In another embodiment, the R base has 1 to 4 carbon atom.In another embodiment, R ' group has 2 to 4 carbon atoms.In another embodiment, the PAVE monomer comprise perfluor (methylvinylether) (PMVE), perfluor (ethyl vinyl ether) (PEVE), perfluor (propyl vinyl ether) (PPVE) and perfluor (butyl vinyl ether) (PBVE).Can use some PAVE monomers to prepare described multipolymer, as the TFE/PMVE/PPVE multipolymer, manufacturers is called MFA sometimes.

In another embodiment, (per) fluoropolymer comprises the TFE/HFP multipolymer, and wherein the content of HFP is about 5-17 weight %.In another embodiment, (per) fluoropolymer is TFE/HFP/PAVE, and wherein PAVE is PEVE or PPVE, and wherein HFP content is about 5-17 weight %, and PAVE content is about 0.2-4 weight %, and surplus is TFE, to the multipolymer of totally 100 weight %.No matter whether have the 3rd comonomer, the TFE/HFP multipolymer all is called FEP usually.In another embodiment, (per) fluoropolymer is the TFE/PAVE multipolymer of so-called PFA, described multipolymer has the PAVE of the total weight percent of accounting at least about 2 weight %, and when PAVE was PPVE or PEVE, described multipolymer comprised the PAVE of about 2-15 weight % usually.In another embodiment, PAVE in the (per) fluoropolymer comprises PMVE, the described perfluor (methylvinylether) of about 0.5-13 weight % and the PPVE of about 0.5-3 weight % of consisting of, and the surplus among the totally 100 weight % is TFE, and as mentioned above, can be referred to as MFA.

The example of the available (per) fluoropolymer of commercially available acquisition comprises Teflon

100 grades of FEP, TE9494 level and 100J level, and Teflon

(all these (per) fluoropolymers are by E.I.du Pont de Nemours﹠amp for PFA 340n level; Co. (Wilmington DE) buys).

19. the thickness of multi-layer product layer

The thickness that comprises each layer of multiwalled goods is not limit, and the those of ordinary skill in field is determined according to the type used that goods are intended to use thus, and need not the over-drastic experiment.

Multi-layer product of the present invention can have multiple size and configuration.The first layer (A) can be thick or thin, can be rigidity or flexibility, can be smooth or contoured, or the like.The first layer (A) can be rigid disk, flexible sheets or as the structure of container (for example groove jar) or pipe, fiber, electron device (for example printed circuit board (PCB)) or the like.

Multi-layer tubes will be used for another embodiment of supply of fuel therein, and the internal diameter of tubing can be about 3 to about 20mm scope, and the tube wall thickness degree can be about 0.5 to about 2mm scope.

In another embodiment, wherein multi-layer tubes will be used for supply of fuel, and described multi-layer tubes has the first layer (A), the second layer (B) that comprises the FG-fluoropolymer that comprises the nonfluorinated polymers with polar functional group and the 3rd layer (B1) that comprises (per) fluoropolymer, described (B1) layer can thick about 0.05mm about 0.5mm extremely, described (B) layer can thick about 0.05mm to about 0.5mm, and described (A) layer can thick about 0.05mm about 1.5mm extremely.

20. prepare the method for multi-layer product

In one embodiment, described multi-layer product can be made by a kind of method, and described method comprises lamination the first layer (A) sheet material and comprises the second layer (B) sheet material of FG-fluoropolymer.

In another embodiment, described multi-layer product can be made by a kind of method, and described method comprises the first layer (A) vapor deposition to the second layer that comprises the FG-fluoropolymer (B) sheet material.

In another embodiment, multi-layer product can be made by a kind of method, described method comprises FG-fluoropolymer electrostatic powder is coated in the substrate (nonfluorinated polymers, metal or the inorganics that for example have polar functional group), forming the substrate of powder coated, and the substrate of heating described powder coated is to form multi-layer product.

In another embodiment, multi-layer product can be made by a kind of method, described method comprises FG-fluoropolymer powder dispersion liquid is coated in the substrate (nonfluorinated polymers, metal or the inorganics that for example have polar functional group), and heat the substrate that described liquid applies, to form described multi-layer product.In this embodiment, can use known powder dispersion liquid coating method, as authorize among people's such as Hagiwara the EP patent 0789728B1 disclosed.

In another embodiment, multi-layer product can be made by a kind of method, described method comprises FG-fluoropolymer water dispersion is coated in the substrate (nonfluorinated polymers, metal or the inorganics that for example have polar functional group), and heat the substrate that described dispersion applies, to form described multi-layer product.In this embodiment, can use known aqueous dispersion coating method, as authorize in the United States Patent (USP) 3,925,292 of Holmes disclosed.

In another embodiment, multi-layer product can be made by a kind of method, described method comprises FG-fluoropolymer rotation is coated with and serves as a contrast in the substrate (nonfluorinated polymers, metal or the inorganics that for example have polar functional group), and heat the substrate that described rotation is coated with lining, to form described multi-layer product.In this embodiment, can use known Rotolining process, as authorize in people's such as Nishio the U.S. Pat 6,287,632 disclosed.

In another embodiment, can be by sheet material to be extruded, the formation layered product that at high temperature sheet material forced together then forms described multi-layer product.Can make this type of layered product be molded into different shape by currently known methods then with commercial use, as: flexible pipe, pipeline, hard tube, thin slice, capping, packing ring, filler, film, groove jar, roller, bottle and container.

In another embodiment, optional the 3rd layer (B1) that comprises the second layer (B) of FG-fluoropolymer and comprise (per) fluoropolymer can be coextruded on the first layer (A) that comprises metal, the feasible the first layer (A) and the second layer (B) adjacency that comprises the FG-fluoropolymer that comprises metal, thereby make the first layer (A) and the second layer (B) bonding with enough persistent layer bounding forces, and form for example insulated line.

In another embodiment, can extrude form layers (A) sheet and layer (B) sheet and optional layer (B1) sheet, by the formation layered product that at high temperature described sheet material forced together, make described multi-layer product then by sheet material.Can make this type of layered product be molded into different shape by currently known methods then with commercial use, as: flexible pipe, pipeline, hard tube, thin slice, capping, packing ring, filler, film, groove jar, roller, bottle and container.

In another embodiment, can be with optional the 3rd layer of (B1) coextrusion that comprises the first layer (A) of nonfluorinated polymers and comprise the second layer (B) of FG-fluoropolymer and comprise (per) fluoropolymer with polar functional group, make layer (A) and layer (B) adjacency, and layer (B) and layer (B1) adjacency, thereby make layer (A) bonding with enough persistent layer bounding forces, and form the stratiform pipe with layer (B).

So the those of ordinary skill in field will be recognized, the concrete composition that this enough persistent layer bounding force depends on extrusion condition and comprises the material of different layers.This condition can comprise temperature, rate of extrusion, stretch rate, stretching equilibrium ratio, interfacial pressure, rate of cooling, cooling conditions (keep-uping pressure as cooling period) etc., and may be subjected to the influence that equipment is selected, as mandrel length, die head characteristics (comprising cutting edge length) etc.

In one embodiment, enough persistent layer bounding force makes layer (A) and layer (B) is bonding and be meant, for having the multi-layer product (for example forming) of layer (A) and layer (B) by coextrusion, layer (A) and layer (B) are bonded to each other, make under the condition that is lower than layer (A) and/or layer (B) yield strength layering not to take place.

The first layer (A) comprises in the embodiment of metal therein, the feasible the first layer (A) and bonding being meant of the second layer (B) that comprises the FG-fluoropolymer that comprises metal of enough persistent layer bounding force, for comprising the multi-layer product of metal and FG-fluoropolymer, metal level and FG-fluoropolymer layer are bonded to each other, make the stripping strength of multi-layer product greater than about 50g/in.

Embodiment

Notion described herein will further describe in the following example, and described embodiment is not limited in the scope of describing in the claim of the present invention.

Embodiment 1: the FG-fluoropolymer that comprises TFE, HFP, PMVE and maleic anhydride

The preparation of FG-fluoropolymer

This embodiment shows by continuation method and prepares the FG-fluoropolymer, and described FG-fluoropolymer comprises the repeating unit from TFE, HFP, PMVE and maleic anhydride.

As United States Patent (USP) 6,051, make up reaction system described in Fig. 1 of 682, have following replenishing simultaneously.The structure high-pressure piston pump is directly accurately to be pumped into liquid in the vertical autoclave of stirring.The fluid of pumping is the mixture of solvent and dissolved maleic anhydride.Any fluid that can dissolve maleic anhydride and excessively not telomerize all is applicable to this purpose.This kind solvent includes but not limited to ethyl acetate, acetone and Glacial acetic acid.In this embodiment, the maleic anhydride mixture is made up of the 20 gram maleic anhydrides that are dissolved in the 100 gram ethyl acetate.

With pure CO ₂The vertical autoclave that purge to stir link to each other with all feed, filtration and circulating system are to remove all moisture and air.Monomer feed stream is set, make form roughly with steady state operation during to leave the composition of reactor identical.Monomer and CO ₂As follows with the weight ratio of TFE: CO ₂/ TFE=0.95 to 1.0, HFP/TFE=4.7 to 4.8, and PMVE/TFE=0.75 to 0.8.TFE content in this mixture is about 13.2 weight %.Reactor content is heated to 65 ℃ service temperature, and, reactor is risen to the 8.3MPa working pressure by adding this monomer mixture.After reaching working pressure, open the reactor content stream by reactor outlet and send by filtration system and cycle back to the feed system.The controlling reactor effluent makes that the residence time of material in reactor is about 45 minutes.By the monomer feed flow control reactor pressure that flows to reactor.Being used for this initiator of polyreaction is the HFPO dimer peroxide (CF of nominal 10 weight % ₃CF ₂CF ₂OCF (CF ₃) (C=O) OO (C=O) (CF ₃) CFOCF ₂CF ₂CF ₃, make by the method in the United States Patent (USP) 6,395,937 for example) and at Vertrel Mixture among the XF (2,3-dihydro perflenapent derives from E.I.du Pont de Nemours).By every liter of reactor volume of preload 5mL initiator solution, make the reaction beginning, and, keep reaction by injecting every liter of reactor volume of 4mL/hr initiator solution continuously.Behind initiator liquid stream beginning feed, change feed and form, make monomer and CO ₂As follows with the weight ratio of TFE: CO ₂/ TFE=0.5, HFP/TFE=2.9 to 3.0, PMVE/TFE=0.47 to 0.48.TFE content in this mixture is about 20.2 weight %.When initiator liquid stream beginning feed, also begin the maleic anhydride solution pump to be delivered in the reactor with the speed of every liter of reactor volume of 0.5mL/hr.When polyreaction reaches stable state, make the FG-fluoropolymer with the speed of every liter of reactor volume of 85 to 100 gram/hr.Control FG-fluoropolymer viscosity by changing the initiator flow.

(DSC) records by differential scanning calorimetry, and the FG-fluoropolymer that makes has 245 ℃ fusing point.The polymer composition that is recorded by FTIR has the HFP content of 5.3 weight %, the PMVE content of 6.3 weight % and the maleic anhydride content of 0.035 weight %.Use the 5kg counterweight down at 297 ℃, the MFR that is recorded by ASTM method D1238-04c is 22g/10min.

Characteristic

A) fuel vapours transfer rate

From having the 0.35mm nominal thickness and being used for the film of penetration testing, downcut circular sample with 36mm minimum diameter.Use the method for describing among the SAE J2659-03 " Test Method to measure Fluid Permeation of Polymeric Materials by Speciation " to obtain permeation data, Details as Follows:

The penetration testing pond is a feature with two fuel bowls of being made by glass and separating with testing film.Use two to be encapsulated in the fluoro-containing copolymer film and to put into the O shape type packing ring that makes by fluoroelastomer in the fuel bowl flange groove, testing film is fixed between two fuel bowls.

Test liquid is CE 10 fuel (10 weight % ethanol, 45 weight % octane-iso, 45 weight % toluene), and described fuel is put in the end cup, and the vapour space is lower than described film.(about FG-fluoropolymer fuel vapours transfer rate, referring to part 6 above.) test pool is put in the chamber that is controlled at 40 ℃ ± 1 ℃.The adjustment time that employing changed between 103 to 122 days is to guarantee that sample and fuel reach balance before beginning the infiltration measurement.Thin-film material and film thickness are depended in the change of adjustment time.Adopt certain adjustment time, so that film reached stable state or constant flux rate before beginning the infiltration measurement.The adjustment period between CE10 fuel is upgraded, to keep fuel composition.(when the permeate substance flux rate is constant, determine the adjustment time.Flux rate is subjected to the influence of film thickness and polymer type, so each film may need the different adjustment time.Repeat samples is put in the CE10 fuel, under 40C, adjusted.The adjustment time of repeat samples is shown in the following table 1.)

The HP 5890 type gas chromatographs that use is made by Hewlett Packard separate and analyze each component of fuel in the sweep gas.

By to the sampling of penetrant/sweep gas mixture, determine the steady state flux of every kind of fuel element, and by the contribution with all different fuel components add and, obtain to see through the total flux of described film.By film thickness be multiply by steady state flux, obtain vapor transmission speed VTR.

With sample replication twice, and independent component vapor transmission speed and total vapor transmission speed is reported in the following table 1 with the form of measuring mean value for twice.

Table 1

B) adhesion results of the tubing/layered product of coextrusion

From the tubing of coextrusion with the pipe bar of one inch wide of vertical cutting.Locate layer to be separated or attempt separation in the bed interface, and under room temperature and 50% humidity, in tensile tester, with " the T type is peeled off " configuration, with the segregation rate pulling of 12 inch per minute clocks (about 30cm/min).With the mean force of the separating layer width divided by the pipe bar, obtaining with gram/inch is the stripping strength that unit reports.Carry out three times or five times and independently measure, and report with mean value.Begin test if layer is separated, then the result is reported to " CNS " or " can't separate ", and the adhesive bond of expression top.Peel strength value is higher than 680 gram/inches, thinks tackiness agent.Result in the table 2 shows, thermoplastics such as polymeric amide or the DuPont of the polymer composition among the embodiment 1 to having amine functional group ETPV EX23 has excellent bounding force (being stripping strength).

Table 2

Result in the following table 3 shows that the polymer composition among the embodiment 2A has good bounding force (being stripping strength) to thermoplastics such as the polymeric amide with amine functional group.

Table 3

Layer 1	Layer 2	Average stripping strength, gram/inch
			The FG-fluoropolymer of embodiment 2A	PA12	283.9(721)

Result in the table 4 shows that the polymer composition among the embodiment 3 (A-E) has good bounding force (being stripping strength) to thermoplastics such as the polymeric amide with amine functional group.

Table 4

Layer 1	Layer 2	Average stripping strength, gram/inch
			The FG-fluoropolymer of embodiment 3A	PA12	717.3(1,822)
The FG-fluoropolymer of embodiment 3B	PA12	419.7(1,066)
			The FG-fluoropolymer of embodiment 3C	PA12	500.4(1,271)
The FG-fluoropolymer of embodiment 3D	PA12	471.7(1,198)
			The FG-fluoropolymer of embodiment 3E	PA12	644.1(1,636)

Embodiment 2: the FG-fluoropolymer that comprises TFE, HFP, PEVE and methylene-succinic acid

The preparation of FG-fluoropolymer

To the L/D ratio rate be about 1.5 and the capacity of being filled with water be having in the cylindrical stainless steel reactor of horizontal that water jacket, slurry formula stir of 10 gallons (37.9L), add ammonium perfluorocaprylate water phase surfactant mixture and the 5g Krytox of 50 pounds of (22.7kg) softening waters, 330mL 20 weight %

157FSL (per) fluoropolymer carboxylic acid.The reactor blade stirs with the speed of 46rpm, and reactor is heated to 60 ℃, and emptying also purges three times with TFE.Temperature of reactor is increased to 103 ℃ then.When temperature 103 ℃ locate stable after, it is 444psig (3.16MPa) that HFP is slowly added in the reactor until pressure.92 milliliters liquid PEVE is injected in the reactor.Subsequently TFE is joined in the reactor to realize the resulting pressure of 645psig (4.55MPa).Then the freshly prepared initiator solution that comprises 1.63 weight % ammonium persulphates (APS) of 40mL is joined in the reactor.Next, initiator solution that this is identical is pumped into the speed of 10mL/min and is used for remaining polyreaction in the reactor.After having begun, in reactor, add extra TFE with the speed of 24.5 pounds of (11.1kg)/125min by the polyreaction shown in 10psi (70KPa) reactor pressure decrease.In addition, add liquid PEVE with the speed of 1.0mL/min in entire reaction in the stage.After polyreaction begins, added after 1 pound of (0.45kg) TFE, begun to add methylene-succinic acid (ITA) aqueous solution of 1 weight %, and continued always at the remainder of this batch reaction with the speed of 5mL/min.After having injected 24.4 pounds of (11.1kg) TFE between 125 minute reaction period, termination reaction.Last in step of reaction, stop TFE charging, PEVE charging and initiator feed, and cooling reactor while stirring.When the temperature of reactor content reaches 90 ℃, with the slow exhaust of reactor.After being vented near normal atmosphere, with the nitrogen purging reactor to remove residual monomer.Further after the cooling, under 70 ℃, dispersion is given off by reactor.After the coagulation, by filtering separation polymkeric substance and dry in 150 ℃ convection heat air chest subsequently.Use the 5kg counterweight to record by ASTM method D1238-04c down at 372 ℃, described polymkeric substance has the melt flow rate (MFR) of 34.7g/10min, 234 ℃ fusing point and the HFP content of 13.9 weight %, the PEVE content of 1.69 weight % and the methylene-succinic acid content of 0.05 weight %.

By four kinds of FG-fluoropolymer samples of method for preparing, different is methylene-succinic acid (ITA) the rate of injection difference of sample room, to obtain the ITA of Different Weight % as shown in table 5.

Table 5

Embodiment 3:FG-fluoropolymer: TFE/HFP/PEVE/ methylfumaric acid

The preparation of FG-fluoropolymer

To the L/D ratio rate be about 1.5 and the capacity of being filled with water be having in the cylindrical stainless steel reactor of horizontal that water jacket, slurry formula stir of 10 gallons (37.9L), add the nitric acid of 50 pounds of (22.7kg) softening waters, 500mL 0.1N, ammonium perfluorocaprylate water phase surfactant mixture and the 2g Krytox of 260mL 20 weight %

157FSL (per) fluoropolymer carboxylic acid.The reactor blade stirs with the speed of 46rpm, and reactor is heated to 60 ℃, and emptying also purges three times with TFE.Temperature of reactor is increased to 103 ℃ then.When temperature 103 ℃ locate stable after, it is 444psig (3.16MPa) that HFP is slowly added in the reactor until pressure.92 milliliters liquid PEVE is injected in the reactor.Subsequently TFE is joined in the reactor to realize the resulting pressure of 645psig (4.55MPa).Then the freshly prepared initiator solution that comprises 2.38 weight % ammonium persulphates (APS) of 50mL is joined in the reactor.Next, initiator solution that this is identical is pumped into the speed of 10mL/min and is used for remaining polyreaction in the reactor.After having begun, in reactor, add extra TFE with the speed of 15 pounds of (6.8kg)/125min by the polyreaction shown in 10psi (70KPa) reactor pressure decrease.In addition, add liquid PEVE with the speed of 1.0mL/min in entire reaction in the stage.After polyreaction begins, added after 1 pound of (0.45kg) TFE, begun to add methylfumaric acid (MAS) aqueous solution of 1 weight %, and continued always at the remainder of this batch reaction with the speed of 5mL/min.After having injected 15 pounds of (6.8kg) TFE between 125 minute reaction period, termination reaction.At last stage reaction, stop TFE, PEVE, initiator solution and methylfumaric acid solution feed, and make reactor cooling, keep simultaneously stirring.When the temperature of reactor content reaches 90 ℃, with the slow exhaust of reactor.After being vented near normal atmosphere, with the nitrogen purging reactor to remove residual monomer.Further after the cooling, under 70 ℃, dispersion is given off by reactor.After the coagulation, by filtering separation polymkeric substance and dry in 150 ℃ convection heat air chest subsequently.Use the 5kg counterweight to record by ASTM method D1238-04c down at 372 ℃, described polymkeric substance has the melt flow rate (MFR) of 79.6g/10min, 224 ℃ fusing point and the HFP content of 16.5 weight %, the PEVE content of 1.19 weight % and the methylfumaric acid content of 0.031 weight %.

By four kinds of FG-fluoropolymer samples of method for preparing, different is to make the TFE feeding rate be changed to about 76g/min from about 36g/min by regulating TFE pressure, to obtain the result shown in the table 6.

Table 6

The FG-fluoropolymer of following research embodiment 1 (comprising repeating unit) and Kapton from TFE, HFP, PMVE and maleic anhydride

Bonding:

The polymeric aggregate of equivalent is placed between the square Kapton of two 5cm (2in).The Kapton that will comprise polymeric aggregate then is placed between 20cm (8in) the square-shaped metal pressing plate.Then pressing plate is placed in the platen press that is preheated to 310 ℃ or 360 ℃.Pressing plate was placed 3 minutes in the platen press of heat, and do not applied any pressure.Then to pressing plate apply 2 minutes 137MPa (20, pressure 000psi).Relief pressure then, and pressing plate taken out from platen press, and make it be cooled to room temperature.Then peel off Kapton, and assess bounding force with 1 to 10 relative scale, the 10th, separate Kapton sheet the highest required relative power, the 1st, separate the required minimum power relatively of Kapton sheet.The result is contained in the following table 7.

Table 7

1.FEP TE9494﹠amp; FEP TE9495: the multipolymer of tetrafluoroethylene and R 1216 derives from E.I.du Pont de Nemours﹠amp; Co. (Wilmington, DE).

2.Kapton

: Kapton derives from E.I.du Pont de Nemours﹠amp; Co. (Wilmington, DE).

The FG-fluoropolymer of following research embodiment 1 (comprising the repeating unit from TFE, HFP, PMVE and maleic anhydride) is bonding with various metals.

The polymeric aggregate of equivalent is placed between two 5cm (2in) square-shaped metal paper tinsel.The tinsel that will comprise polymeric aggregate then is placed between 20cm (8in) the square-shaped metal pressing plate.Then pressing plate is placed in the platen press that is preheated to 310 ℃ or 360 ℃.Pressing plate was placed 3 minutes in the platen press of heat, and do not applied any pressure.Then to pressing plate apply 2 minutes 137MPa (20, pressure 000psi).Relief pressure then, and pressing plate taken out from platen press, and make it be cooled to room temperature.Follow the stripping metal paper tinsel, and assess bounding force with 1 to 9 relative scale, the 9th, separate paillon foil the highest required relative power, the 1st, separate the required minimum relative power of paillon foil.The result is contained in the table 8.

Table 8

1.FEP TE9494﹠amp; FEP TE9495: the multipolymer of tetrafluoroethylene and R 1216 derives from E.I.du Pont de Nemours﹠amp; Co. (Wilmington, DE).

2. Copper Foil: Puratronic high purity research chemical substance, 0.1mm is thick, 99.999% (based on the copper metal), stock number 42189, lot number C31K22.

3. aluminium foil: aluminium alloy, (East Alton IL), comprises the aluminium of 81-99 weight % to derive from Olin Brass and Winchester.

4.Monel paper tinsel, derive from Lyon Industries (South Ilgin, IL), 0.025mm Monel liner.

The FG-fluoropolymer of embodiment 1 demonstrates than the more excellent bounding force of the FEP that does not contain FG (hexafluoropropylene (HFP)/tetrafluoroethylene (TFE)) polymkeric substance all test metals.

Embodiment 6: the FG-fluoropolymer of embodiment 1 and aluminium bonding

The FG-fluoropolymer of following research embodiment 1 (comprising the repeating unit from TFE, HFP, PMVE and maleic anhydride) is bonding with aluminium.

The square equal thickness polymer membrane of 10cm (4in) is placed between the square aluminium foil of two 15cm (10in).The tinsel that will comprise polymer sheet then is placed between the metal platen.Then pressing plate is placed in the platen press that is preheated to selected temperature.Then 17MPa (2,500psi) exert pressure down, pressing plate was placed 5 minutes in the platen press of heat.Relief pressure then, and pressing plate taken out from platen press, and make it be cooled to room temperature.Follow the stripping metal paper tinsel, and assess bounding force with 1 to 4 relative scale.The no bounding force of 1 expression, sheet material is easy to peel off from polymkeric substance, the certain bounding force of 2 expressions, 3 expression strong adhesive powers, and 4 expression sheet materials can't separate.The result is contained in the table 9:

Table 9

1. the multipolymer of perfluorination ethylene-propylene (FEP) and perfluoroalkoxy (PFA) derives from E.I.du Pont de Nemours﹠amp; Co. (Wilmington, DE).Numeral after FEP or the PFA name relates to the metering thickness of film.For example, FEP 200C20 is that thickness is the film of 200 (2 mils)." C " after FEP or the PFA name relates to " can be bonding " film that corona treatment is crossed under acetone/nitrogen environment.

2. manual corona treatment: with aluminium foil combination and hot pressing before, make film on both direction, experience 6 scanning with the hand-held corona unit.

The FG-fluoropolymer of embodiment 1 shows excellent bounding force result under low-down temperature.

Embodiment 7: the FG-fluoropolymer powder coating of embodiment 1 and aluminium, cold-rolled steel and stainless steel Bonding

Use Nordson Versaspray II electrostatic powder paint gun that the polymkeric substance electrostatic powder is coated on the ready metal sheet, and in the baking oven of hot-air convection, heat, until obtaining level and smooth coating.Metal sheet is aluminium, cold-rolled steel and stainless steel, and before powder coated, uses solvent cleaned, and handles with 1/2 sand grains frosted.Under 274 ℃ and 288 ℃, carry out 15 minutes by a definite date hot humid test twice.The gained coat-thickness is 1.5 to 3.5 mils.

According to ASTM D3359 method B program, measure the bounding force of coating.With the coating crosscut, in water, boil then and boil 15 minutes.

For all test metals, no matter be smoothly or frosted handle, under two solidification values, the coating of the FG-fluoropolymer of embodiment 1 (comprising the repeating unit from TFE, HFP, PMVE and maleic anhydride) all obtains 5B grade (0% is removed).

(perfluorination ethylene-propylene polymkeric substance derives from E.I.du Pont de Nemours﹠amp to the low melt FEP powder coating of comparison polymer 532-8000; Co. (Wilmington, DE)) obtains the bounding force test result (being removed greater than 65%) of 0B on the level and smooth metal that frosted is not handled, and obtains the bounding force test result (0% is removed) of 5B on the metal that frosted is handled.Under two solidification values, all metals are obtained identical result.

The FG-fluoropolymer of embodiment 1 shows excellent bounding force result to untreated level and smooth metallic surface.

Embodiment 8: the extrusion die that is coated with the FG-fluoropolymer of embodiment 1

Known, fused Teflon

The FEP resin will be during at a high speed extruding processing melt fracture.At Teflon

In PFA and the High molecular weight polyethylene, also observe melt fracture.Melt fracture is worthless phenomenon, its available capillary rheometer research.

Use Dynisco LCR6000 type Kayeness capillary rheometer to come the extruding polymerization matter sample, it is that 0.03 inch and slenderness ratio are 20 DyniscoY300-20 circle die head that described capillary rheometer has diameter.

In an experiment, at first, clean described die head by in 570 ℃ of ashing furnaces, heating.The cleaning sample chamber is made as 380 ℃, is written into the FG-fluoropolymer (comprising the repeating unit from TFE, HFP, PMVE and maleic anhydride) of embodiment 1 then.Make the FG-fluoropolymer by the die orifice flow passage, be coated with the FG-fluoropolymer layer until flow passage.From the sample chamber, remove the FG-fluoropolymer then, and adding FEP TE9494 (does not comprise perfluorination ethylene-propylene (FEP) multipolymer of FG, derives from E.I.du Pont de Nemours﹠amp in the sample chamber; Co. (Wilmington, DE)).FEP TE9494 sample was heated in the sample chamber six minutes.At 13.9l/s to 1, implement under the range of shear rate of 413l/s to analyze.Collect extruding of FEP TE9494 and restraint section, and the melt fracture of research on the bundle section surface.

In control experiment, at first, clean described die head by in 570 ℃ of ashing furnaces, heating.The cleaning sample chamber is made as 380 ℃, and (perfluorination ethylene-propylene (FEP) multipolymer derives from E.I.du Pont de Nemours﹠amp to be written into FEP TE9494 then; Co. (Wilmington, DE)).The FEPTE9494 sample was heated in the sample chamber six minutes.At 13.9l/s to 1, implement under the range of shear rate of 413l/s to analyze.Collect extruding of FEP TE9494 and restraint section, and the melt fracture of research on the bundle section surface.

Successive analysis is implemented in each experiment twice, and the condition of generation melt fracture is obviously identifiable.After with FG-fluoropolymer pre-treatment die head, FEPTE9494 is extruded enforcement five times with 5 hours intervals.Observe, melt fracture continues to improve during this period.What obtain the results are shown in the table 10.

Table 10

This embodiment illustrates, and the melt extrusion die head that is coated with the FG-fluoropolymer can make Teflon The FEP extrudate stands higher processing speed, and does not form melt fracture.

Notice, above general describe or embodiment described in behavior not all is necessary, a part of concrete behavior is optional, and those, also can implement one or more other behaviors except described.In addition, the order of listed behavior needs not to be the order of implementing them.

In above-mentioned specification sheets, with reference to specific embodiment different concepts has been described.Yet those of ordinary skill in the art recognizes, under the situation that does not break away from the scope of the invention as hereinafter described in the claims, can carry out various modifications and variations.Therefore, it is illustrative and nonrestrictive that specification sheets is considered to, and all these type of modification are intended to be included in the scope of the present invention.

The solution of beneficial effect, other advantages and problem has above been described in conjunction with specific embodiment.Yet, the solution of beneficial effect, advantage, problem and can cause any beneficial effect, advantage or solution produces or the more significant any feature that becomes may not be interpreted as the key of any or all claim, essential or essential characteristic.

Will be appreciated that for clarity sake, some characteristic described in the context of this paper different embodiments also can provide with array mode in single embodiment.Otherwise for simplicity, a plurality of characteristics described in single embodiment context also can provide respectively, or provide in the mode of any sub-portfolio.In addition, the correlation values of describing in the scope comprises each value in the described scope.

Claims (21)

1. the hemicrystalline fluoropolymer of melt-processable, described fluoropolymer comprises:

(a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %;

(b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %; With

(c) repeating unit from tetrafluoroethylene of all the other weight percents.

2. the hemicrystalline fluoropolymer of the melt-processable of claim 1, described fluoropolymer comprises:

(a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %;

(b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %;

(c) about 0.5 weight % is to the repeating unit from perfluor (alkyl vinyl ether) of about 10 weight %; With

(d) repeating unit from tetrafluoroethylene of all the other weight percents; Wherein from the repeating unit weight percent of R 1216 with from the repeating unit weight percent sum of perfluor (alkyl vinyl ether) greater than about 4 weight % and less than about 20 weight %.

3. the hemicrystalline fluoropolymer of the melt-processable of claim 1, described fluoropolymer comprises:

(a) about 4 weight % are to the repeating unit from R 1216 of about 14 weight %;

(b) about 0.001 weight % to about 1 weight % from having carboxyl and polymerizable carbon-to-carbon double bond and comprising the di-carboxylic acid anhydride group or the repeating unit of the hydrocarbon monomer of di-carboxylic acid group;

(c) about 0.5 weight % is to the repeating unit from perfluor (alkyl vinyl ether) of about 3 weight %; With

(d) repeating unit from tetrafluoroethylene of all the other weight percents.

4. the hemicrystalline fluoropolymer of claim 1 or 2 melt-processable, the described hydrocarbon monomer that wherein has carboxyl and polymerizable carbon-to-carbon double bond comprises di-carboxylic acid anhydride group or di-carboxylic acid group.

5. the mixture of melt blending, described mixture comprises the hemicrystalline fluoropolymer of polymkeric substance and melt-processable, and the hemicrystalline fluoropolymer of wherein said melt-processable comprises:

(a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %;

(b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %; With

(c) repeating unit from tetrafluoroethylene of all the other weight percents.

6. multi-layer product, described goods have the layer of the hemicrystalline fluoropolymer that comprises melt-processable, and the hemicrystalline fluoropolymer of wherein said melt-processable comprises:

(a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %;

(b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %; With

(c) repeating unit from tetrafluoroethylene of all the other weight percents.

7. the multi-layer product of claim 6, described goods comprise the hemicrystalline fluoropolymer layer and the stratum basale of described melt-processable, and the material that wherein constitutes described stratum basale comprises functional group, and described functional group associates or bonding with the carboxyl of the described hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond.

8. multi-layer product, described multi-layer product comprises:

(A) comprise the first layer of at least a material, described material is selected from nonfluorinated polymers, metal and the inorganics with polar functional group; With

(B) comprise the second layer of the hemicrystalline fluoropolymer of melt-processable, the hemicrystalline fluoropolymer of wherein said melt-processable comprises:

(a) about 2 weight % are to the repeating unit from R 1216 of about 20 weight %;

(b) about 0.001 weight % is to the repeating unit from the hydrocarbon monomer with carboxyl and polymerizable carbon-to-carbon double bond of about 1 weight %; With

(c) repeating unit from tetrafluoroethylene of all the other weight percents,

Wherein (A) and (B) adjacency.

9. the multi-layer product of claim 8, wherein said the first layer comprises the nonfluorinated polymers with polar functional group, and wherein said polar functional group is at least a following functional group that is selected from: amine, acid amides, imide, nitrile, carbamate, chlorine root, ether, ester, hydroxyl, carbonate and carboxyl.

10. the multi-layer product of claim 8, the described nonfluorinated polymers that wherein has polar functional group is at least a following nonfluorinated polymers that is selected from: ethylene-propylene acetoacetic ester, ethylene-methyl acrylate, polythene-ethenol multipolymer, polymeric amide, polyethylene terephthalate, polyimide, polymethylmethacrylate, polyvinyl acetate, polyvinyl alcohol, polycarbonate, polyvinyl butyral acetal, urethane, polyacrylonitrile and polyvinyl chloride.

11. the multi-layer product of claim 8, wherein said the first layer comprises metal, and wherein said metal is selected from aluminium, chromium, cobalt, copper, iron, manganese, molybdenum, nickel, niobium, rhenium, steel, tantalum, titanium, tungsten and zirconium.

12. the multi-layer product of claim 8, wherein said the first layer comprises inorganics, and wherein said inorganics is selected from silicate, carbonate, vitriol, halogenide, oxide compound and sulfide.

13. layering does not wherein take place in the multi-layer product of claim 8 under the situation of the yield strength that is lower than the described the first layer (A) and/or the described second layer (B).

14. the multi-layer product of claim 8, wherein said the first layer comprises metal, and the stripping strength of wherein said multi-layer product is greater than about 50g/in.

15. the multi-layer product of claim 8, described goods also comprise the 3rd layer (B1) that contains (per) fluoropolymer, wherein said the 3rd layer (B1) and the described second layer (B) adjacency.

16. the multi-layer product of claim 8, wherein said multi-layer product are multilayered tube, described multilayered tube comprises:

(A) comprise the first layer of described nonfluorinated polymers, and described the first layer is adjacent to polar functional group;

(B) comprise the second layer of the hemicrystalline fluoropolymer of described melt-processable;

Wherein said layer arranged in co-axial alignment makes described the first layer (A) in the outside of the described second layer (B), and the inner face adjacency of the outside of the described second layer (B) and described the first layer (A).

17. the multi-layer product of claim 16 is wherein recorded by the method for describing among the SAE J2659-03,40 ℃ down the hemicrystalline fluoropolymer of described melt-processable have and be not more than about 0.1gmm/m ²It CE10 fuel vapours transfer rate.

18. the multi-layer product of claim 16, described goods also comprise the 3rd layer (B1) that contains (per) fluoropolymer, wherein said layer arranged in co-axial alignment makes described the 3rd layer (B1) in the described second layer (B) inboard, and the inner face adjacency of the outside of described the 3rd layer (B1) and the described second layer (B).

19. the multi-layer product of claim 8, wherein said multi-layer product are insulated line, described insulated line comprises:

(A) comprise the electric wire of metal; With

(B) comprise the layer of the hemicrystalline fluoropolymer of described melt-processable;

Wherein (A) and (B) adjacency.

20. the multi-layer product of claim 8, wherein said multi-layer product are the melt extrusion die head that comprises metal, described die head has the flow passage that the composition of the hemicrystalline fluoropolymer of involved described melt-processable applies.

21. the multi-layer product of claim 8, wherein said multi-layer product are optical fiber, described optical fiber comprises:

(A) comprise the fiber of inorganics substrate; With

(B) comprise the layer of the hemicrystalline fluoropolymer of described melt-processable;

Wherein (A) and (B) adjacency.

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