JP2019509379A - Polyaryletherketone composition and method for coating metal surfaces - Google Patents

Abstract

In the present specification, a polyaryl ether ether composition (C) and a method for using the same are disclosed. The composition comprises a polymer blend [blend (B)] consisting of a first polyaryletherketone (PAEK-1) and a second polyaryletherketone (PAEK-2), where ( PAEK-1) is crystalline and exhibits a melting temperature Tm of 330 ° C. or higher, (PAEK-2) is amorphous or crystalline and exhibits a melting temperature Tm of 315 ° C. or lower, and (PAEK-1) Constitutes a blend (B) of more than 0% by weight. The composition (C) can be used in particular for the production of coated metal surfaces, in particular for the coating of (parts of) wires or electronic devices. [Selection figure] None

Description

CROSS REFERENCE TO PRIOR APPLICATIONS This application is based on US Provisional Patent Application No. 62 / 305,731, filed March 9, 2016, European Patent Application No. 16168380.0, filed May 4, 2016, and 2016. This application claims priority to US Provisional Patent Application No. 62/407911, filed October 13, 2003, the entire contents of which are expressly incorporated herein by reference.

  The present invention relates to a polymer composition and its use, in particular a method for coating metal surfaces with the aforementioned composition. More particularly, the composition is a polyaryletherketone composition having high temperature performance, good chemical resistance, and at the same time high adhesion to metal surfaces and high ductility and toughness.

Polyaryletherketone (PAEK) has the following formula:
(-Ar-X-) and (-Ar'-Y-)
(Where
Ar and Ar ′ are the same or different from each other, and an optionally substituted aromatic divalent group,
X is an electron withdrawing group, typically selected from a carbonyl or sulfonyl group;
Y can be an oxygen atom, a sulfur atom, or an alkylene group,
At least 50% of the repeat units are polymers comprising repeat units having -Ar-C (= O) -Ar'-units).

PAEK, especially polyetheretherketone (PEEK), has the formula:
-[O-Ph-C (O) -Ph-O-Ph]-
(Wherein Ph is each independently a substituted phenylene group), is highly crystalline, has a wide range of needs for high temperature performance and good chemical resistance Used for applications. However, PEEK has poor adhesion to metal and is difficult to use in wire coating or other metal coating applications. High flow PEEK is desirable in 3D printing and other applications that require very low melt viscosity, but tends to be brittle when the melt viscosity is very low.

  Therefore, it is necessary to improve the adhesion to metal, the ductility and toughness of PEEK having high fluidity while maintaining high temperature performance and chemical resistance.

European Patent Application Publication No. 0184458A published on June 11, 1986 (IMPERIAL CHEMICAL INDUSTRIES PLC) has the formula:
-[Ph-O-Ph-C (O) -Ph-O]-
And-[Ph-Ph-O-Ph-C (O) -Ph-O]-
Disclosed is a PAEK containing a repeating unit (wherein Ph is a phenylene moiety) and a process for producing the same. In this document, a polymer (hereinafter referred to as “PEEK-PEDEK”) has good electrical insulation properties and is suitable as an insulating material such as wire and cable coating for use at high service temperatures, for example. I teach that. This document does not teach or suggest blends of PEEK-PEDEK with other polymers.

  US Patent Application Publication No. 20120160829A published on June 28, 2012 (ARKEMA FRANCE) is optionally filled with fibers or other elements that increase the modulus of elasticity, and ferrimagnetic or ferromagnetic conductive particles Disclosed is a polymer composition comprising at least one PAEK. This composition can be used in the manufacture of articles that can be welded by induction in alternating electromagnetic fields. Even though it is stated that the PAEK mixture may have to be used to optimize the properties of the material, the examples only disclose compositions comprising polyetherketoneketone (PEKK) and iron powder. Yes. This patent document does not teach the use of the composition for coating metal surfaces.

U.S. Pat. No. 8,536,265 B published on October 20, 2011 (VICTREX MANUFACTURING COMPANY) discloses PAEK polymer materials, such as PEEK, and composite materials comprising the aforementioned materials. The polymeric material is in the range of 0.05～0.12KNsm ^-2, preferably has a melt viscosity in the range of 0.085~0.095kNsm ^-2 (MV). Even though it is stated that the composite material can comprise one or more of the aforementioned PAEK polymer materials, composite materials comprising only a single type of PAEK material, preferably PEEK, are preferred. PAEK can be used in injection molding or extrusion to produce parts with relatively thin walls. There is no specific disclosure or suggestion of blended materials comprising two or more PAEK polymer materials, no implied use of blends for metallization applications, ductility and toughness while retaining high temperature performance and chemical resistance There is also no teaching on how to improve.

  WO 2013/092492 published on June 27, 2013 (SOLVAY SPECIALTY POLYMERS USA) includes at least one polyaryletherketone (PAEK), polyphenylsulfone (PPSU), polyethersulfone (PESU), polysulfone. A mobile electronic device comprising at least one structural part consisting of a polymer composition (C) comprising at least one aromatic sulfone polymer (SP), such as (PSU) or a mixture thereof, and at least one reinforcing filler.

WO2015 / 019047A, published February 12, 2015, includes a first part and a second part, the second part being in contact with the first part In this case,
(I) the first portion includes a first semi-crystalline polymer and includes a phenylene moiety, a carbonyl moiety, and an ether moiety;
(Ii) The second portion includes the second semicrystalline polymer and includes a phenylene moiety, a carbonyl moiety, and an ether moiety.

The second polymer of this component has a melting temperature (T _m ) that is lower than the melting temperature (T _m ) of the first polymer. According to a preferred embodiment, the first semi-crystalline polymer is PEEK and the second polymer is PEEK-PEDEK. This patent document states that the first and second parts can be fixed together with high strength physicochemical interactions to provide a component that is highly chemically resistant and has long-term mechanical properties. Teaching. The component is made by contacting a first part comprising a first polymer, or a precursor of the aforementioned first part, with a second part comprising a second polymer. Typically, a molten first polymer, optionally including a filler, is overmolded around the second portion. This patent document does not disclose or suggest blends of different PAEKs and their use in metallization applications.

  WO 2015 / 124903A, published August 27, 2015, relates to a sintering process for producing objects using electromagnetic radiation, said process being PEEK-PEDEK. Including the use of polymeric materials, optionally in combination with fillers and radiation absorbers. The polymeric material can be a so-called “virgin PEEK-PEDEK” or a mixture (blend) of virgin and recycled PEEK-PEDEK. This patent document does not disclose a mixture of PEEK-PEDEK and other polymers.

WO2015 / 189567A, published December 17, 2015, includes a first part and a component that includes a second part in contact with the first part (e.g., to the World Wide Web). Part of the electronic device for connecting or communicating), in this case,
(I) the first part comprises PEEK-PEDEK;
(Ii) The second portion includes a metal.
The first portion of the polymer can be part of a composition comprising a polymer and a filler. There is no disclosure or suggestion of compositions comprising PEEK-PEDEK in combination with other PAEKs, not to mention other PAEKs with higher crystallinity.

  WO2015 / 198063A, published December 30, 2015, relates to a polymeric material forming a component comprising a first part and a second part, in this case a third part. Is arranged between the first part and the second part. Each part comprises a polymeric material, ie PAEK. In one embodiment, part A comprises a polymer material (A) that is PAEK and another polymer material (C) that is PEEK-PEDEK. This patent document does not disclose or suggest the use of this composition of part A for metallization applications.

International Publication No. 2016 / 016643A (VICTREX MANUFACTURING LIMITED) published on February 4, 2016 is
A polymer material (A), ie a PEEK-PEDEK polymer;
A polymer material (B), preferably PEEK.

  This blend can also be part of a composition comprising a thermoplastic polymer (C), preferably polysulfone and a fibrous filler. This blend or composition can be used in the manufacture of injection molded or extruded parts.

  No disclosure or suggestion regarding the use of this blend for metal coating is provided.

  WO 2009/058362 A1 (POLYMICS, LTD), published May 7, 2009, relates to a protective film for substrates comprising metal, said film being formed by a polymer base layer and a polymer top layer. And the upper layer has a higher elongation at break and higher crystallinity than the base layer. In particular, Example IV of this document discloses a protective film formed by coextrusion of amorphous PEKK as a base layer and semicrystalline PEEK as an upper layer. This film is applied to an aluminum sheet by pressing and heating at 335 ° C. At this temperature (higher than the melting temperature of amorphous PEKK and lower than the melting temperature of semicrystalline PEEK), the semicrystalline PEEK does not melt while the amorphous PEKK softens and bonds to the aluminum sheet. As a result, a blend of the two polymers, i.e. a homogeneous mixture, is not formed. To obtain a polymer blend, bulk diffusion does not occur when two polymers with different melting temperatures are in contact and heated at a temperature above the temperature of the lowest melting component but below the temperature of the highest melting component. Or the need for a convection process is just known in the art. In view of the fact that the film disclosed in WO2009 / 058362A1 is not a uniform blend, damage to the top layer and exposure of the base layer can adversely affect its protective effect.

EP-A-01138128A1 (April 24, 1985) relates to a blend comprising at least two poly (aryl ether) polymers said to be useful, for example, in electrical wire and connector applications. . The polymer blends disclosed herein have a single crystal melting point (T _m ) and a single glass transition temperature (T _g ). This document does not imply or suggest any mixture of at least two polymers, at least one of which is not crystalline, and further, this document shows high crystallinity by mixing crystalline and amorphous polymers. This level does not teach or suggest that a high level of chemical resistance is maintained.

  US Patent Application Publication No. 2016/0115314 published on April 28, 2016 (ARKEMA FRANCE) relates to a PEEK-based composition comprising a specific amount of PEKK in which PEKK contains a certain ratio of terephthalic acid and isophthalic acid units. . Incorporation of PEKK into a PEEK-based composition has been described to increase two generally competing mechanical properties, yield stress and elongation at break (paragraph, [0071]). It is also described that the crystallization rate is slowed, thereby reducing the internal stress of the material (which eliminates the expensive post-annealing step for a long time) and can obtain an undeformed portion having a desired optimum shape. (Paragraph, [0072]). However, this document does not mention adhesion of the composition to a metal substrate.

DISCLOSURE OF THE INVENTION Applicants have surprisingly found that blends of at least two different PAEK polymers maintain adhesion, toughness, and impact resistance to metal while retaining high strength, temperature performance, and chemical resistance. It has been found that it can be advantageously used in applications where it is necessary to improve the resistance. In particular, Applicants have found that such mixtures can be used for metallization applications.

Accordingly, in one aspect, the present invention relates to a method for coating a metal surface (Method (M)), the method comprising the step of applying a PAEK composition [Composition (C)] to the metal surface; The aforementioned composition is:
A polymer blend [blend (B)] consisting of a first polyaryletherketone (PAEK-1) and a second polyaryletherketone (PAEK-2),
In this case, (PAEK-1) is crystalline, shows a 330 ° C. or higher melting temperature Tm, (PAEK-2) is amorphous or crystalline, shows a melting temperature _{T m} of a 315 ° C. or less The composition (C) contains more than 50% by weight (PAEK-1).

  In another aspect, the present invention relates to a specific blend (B) and composition (C) for carrying out the method (M).

  In a further aspect, the present invention relates to a final article comprising the composition (C) [article (A)], in particular a metal surface coated with the composition (C) [surface (S)] and the aforementioned surface [Article (A ′)]

General DefinitionFor clarity, throughout this application,
- the melting temperature _{T m} of a (PAEK-1) and (PAEK-2) is, ASTM D3418-03, E1356-03, E793-06, in differential scanning calorimeter (DSC) according E794-06, of 20 ° C. / min heating and using a cooling rate, a temperature determined as the peak temperature of the melting endotherm at 2 ^nd heat scan. For the purposes of this description, if a melt endotherm is detected in the second thermal scan, the polymer is crystalline,
-Any reference to each general definition and each general embodiment of the invention includes each specific definition or embodiment included in each general definition or embodiment, unless otherwise indicated. Intended to
-Use of parentheses "()" before and after the name, symbol, or letter of the compound specifying the formula, such as "Blend (B)", "Composition (C)", Formula (JA), etc. Has the sole purpose of better distinguishing its name, symbol, or letter from the rest of the text, so the preceding parentheses can be omitted,
-If a numerical range is displayed, the end of the range is included,
The term “halogen” unless otherwise stated includes fluorine, chlorine, bromine and iodine;
The term “method” is used as a synonym for the process and vice versa;
The adjective “aromatic” means any mononuclear or polynuclear ring group (or moiety) having a number of π electrons equal to 4n + 2 where n is 0 or any positive integer; The aromatic group (or moiety) can be an aryl or arylene group (or moiety)
An “aryl group” is a hydrocarbon consisting of one core from one benzene ring or from one benzene ring fused together by sharing two or more adjacent ring carbon atoms and from one end. It is a valent group. Non-limiting examples of aryl groups are phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, triphenylyl, pyrenyl, and perylenyl groups. The terminal of the aryl group is a free electron of a carbon atom contained in the benzene ring of the aryl group, and in this case, the hydrogen atom bonded to the aforementioned carbon atom is removed. The end of the aryl group can form a bond with another chemical group,
An “arylene group” is a hydrocarbon consisting of one benzene ring or from one core consisting of a plurality of benzene rings fused together by sharing two or more adjacent ring carbon atoms and from two ends. It is a valent group. Non-limiting examples of arylene groups are phenylene, naphthylene, anthrylene, phenanthrylene, tetracenylene, triphenylylene, pyrenylene, and peryleneylene. The terminal of the arylene group is a free electron of a carbon atom contained in the benzene ring of the arylene group, and in this case, the hydrogen atom bonded to the carbon atom is removed. Each end of the arylene group can form a bond with another chemical group.

Polyaryl ether ketone (PAEK-1)
For the purposes of the present invention, the PAEK that constitutes (PAEK-1) is any polymer that contains repeating units (R1), in which case at least 50 mol% of the aforementioned repeating units are Formulas (JA) to (JQ):
(Where:
Each -R 'is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth Selected from the group consisting of metal phosphonates, alkyl phosphonates, amines and quaternary ammonium;
-J 'is zero or an integer from 1 to 4,
-Y 'is an alkylidene group;
Said repeating unit (R1) is in accordance with at least one of the polymers is selected such that the polymer is crystalline and exhibits a melting temperature T _m of 330 ° C.

  In the repeating unit (R1), each phenylene moiety may independently have a 1,2-, 1,4-, or 1,3-bond to another moiety different from R ′ in the repeating unit. it can. Preferably, the aforementioned phenylene moiety has a 1,3- or 1,4-bond, more preferably a 1,4-bond.

  Furthermore, in the repeat unit (R1), j 'is preferably zero at each occurrence, i.e. the phenylene moiety has no substituents other than those that allow attachment in the polymer backbone.

Preferred repeating units (R1) are therefore selected here from those of the following formulas (J′-A) to (J′-Q).

  Advantageously, (PAEK-1) comprises at least 50 mol% of repeating units (JA), (JB), (JC), or (JO). More preferably, (PAEK-1) is at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, most preferably at least 90 mol% of repeating units (J- A), (J-B), (J-C), or (J-O). Typically, the units (JA), (JB), (JC) and (JO) are (J'-A), (J'-B), (J'-C). ) And (J′-O) units.

  Examples of commercially available suitable (PAEK-1) are Solva Specialty Polymers' KetaSpire® PEEK, Evonik's Vestakeep® PEEK, Victrex® Victrex® PEEK, EEK, PE And PEEK-ST, Cytec's Cypek (R) FC, and Cypek (R) HT PEKK.

  In a preferred embodiment, (PAEK-1) is PEEK in which at least 50 mol% of the repeating units are repeating units (JA). Preferably at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, most preferably at least 90 mol%, most preferably at least 95% of the repeating units of (PAEK-1) It is a repeating unit (JA). More preferably, substantially all of the (PAEK-1) repeating units are repeating units (JA).

  In the present application, “substantially all repeating units” means at least 98 mol% repeating units.

Preferred repeating units (JA) are those according to formula (J′-A).
Available from Solvay Specialty Polymers USA when PAEK-1 contains at least 98 mol% units (J′-A), ie under the trademarks KetaSpire® KT-880 NL and KetaSpire® KT-890 NL Excellent results were obtained with PEEK.

Preferably, (PAEK-1) is at least 0.05 kN-s / m ² measured according to ASTM D3835 at 400 ° C. and 1000 s-1 using a 0.5 × 3.175 mm tungsten carbide die. preferably at least 0.07kN-s / ^{m 2,} more preferably shows a melt viscosity of at least 0.08kNs / ^{m 2.}

Preferably, (PAEK-1) is measured according to ASTM D3835 at 400 ° C. and 1000 s−1 using a 0.5 × 3.175 mm tungsten carbide die, at most 0.65 kN-s / m ² , More preferably it exhibits a melt viscosity of at most 0.60 kN-s / m ² , more preferably at most 0.50 kN-s / m ² .

  Preferably, (PAEK-1) is at least 0.4 dL / g, more preferably at least 0.5 dL / g, most preferably at 0.1% in concentrated sulfuric acid at 25 ° C., measured according to ASTM D2857-95 Exhibits an intrinsic viscosity of at least 0.6 dL / g.

  Preferably, (PAEK-1) is measured at 0.1% in concentrated sulfuric acid at 25 ° C., at most 2.0 dL / g, more preferably at most 1.7 dLg /, most preferably at most 1. An intrinsic viscosity of 5 dL / g is shown.

Polyaryl ether ketone (PAEK-2)
For the purposes of the present invention, (PAEK-2) is any polymer that contains the repeating unit (R2), in which case at least 50 mole percent of the aforementioned repeating units are such that PAEK-2 is amorphous. or a crystalline, 315 ° C. is selected as shown below the melting temperature _{T m,} accordance with at least one of the aforementioned formula (J-a) ~ (J -Q).

  In the repeating unit (R2), each phenylene moiety can independently have a 1,2-, 1,4-, or 1,3-bond to another moiety different from R ′ in the repeating unit. . Preferably, the aforementioned phenylene moiety has a 1,3- or 1,4-bond, and more preferably, except for (JA), (JB), and (JQ), 4-bonds, which more preferably independently have 1,3 and 1,4-bonds.

  Further, in the repeat unit (R2), J 'is preferably zero at each occurrence, i.e., the phenylene moiety has no substituents other than those that allow attachment in the polymer backbone.

Accordingly, preferred repeating units (R2) are selected from those of the aforementioned formulas (J′-A) to (J′-Q), and further here the following units (J ″ -A), (J ′ '-B) and (J''-Q)
Selected from.

  In a preferred embodiment of the present invention, (PAEK-2) is a polyaryletherketoneketone (PEKK), i.e., at least 50 mol% of the repeating units of PAEK-2 comprise units (J'-B) and (J ' It is a polymer which is a combination of '-B). Preferably, at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, and most preferably at least 90 mol% of the PEKK repeat units comprise the repeat units (J'-B) and (J '' -B). More preferably, at least 95 mol% of the PEKK repeat units are repeat units (J'-B) and (J "-B). Very good results were obtained with Cypek® DS-E or DS-M PEKK available from Cytec.

  In another preferred embodiment of the present invention, (PAEK-2) comprises PEEK-PEDEK, i.e., at least 50 mol% of the PAEK-2 repeat unit is defined as the repeat unit (J'-A) defined above. It is a polymer which is a combination of (J′-D). Preferably, at least 60 mol%, preferably at least 70 mol%, even more preferably at least 80 mol%, and most preferably at least 90 mol% of the PEEK-PEDEK repeating units comprise the repeating units (J′-A) and ( J′-D). More preferably, at least 95 mol% of the PEEK-PEDEK repeat units are repeat units (J'-A) and (J'-D). Most preferably, all of the PEEK-PEDEK repeat units are repeat units (J'-A) and (J'-D). The PEEK-PEDEK polymer can be prepared according to the method disclosed in the aforementioned European Patent Application Publication No. 0184458A2 of Imperial Chemical Industries PLC. Preferably, the molar ratio of repeating units (J'-A) / (J'-D) is in the range of 65/35 to 85/15. In exemplary embodiments, all repeating units have the following (J′-A) / (J′-D) molar ratios: 65/35, 70/30, 75/25, 80/20, and 85. (J'-A) and (J'-D) units at / 15.

In another preferred embodiment of the invention, (PAEK-2) is sulfonated PEEK, i.e. at least 50 mol% of repeating units, wherein:
PEEK which is a repeating unit (J ′ ″-A) of the formula, and substantially all of the remaining repeating units are repeating units of the formula (J′-A) described above. Sulfonated PEEK can be produced by the sulfonation reaction of PEEK. In particular, sulfonated PEEK in which at least 50 mol% of the repeating units are repeating units (J ′ ″-A) It can be produced by a sulfonation reaction of PEEK in which the repeating unit is a repeating unit (J′-A). For the avoidance of doubt, these preferred (PAEK-2) contain at least 98 mol% of a combination of repeating units (J′-A) and (J ′ ″-A), in which case the repeating units ( J ′ ″-A) comprises at least 50 mol% of all repeating units contained in (PAEK-2).

  In another preferred embodiment of the present invention, at least 50 mol% of the repeating units of (PAEK-2) are repeating units (J'-P). Preferably at least 60 mol%, preferably at least 70 mol%, more preferably at least 80 mol%, most preferably at least 90 mol% of the repeating units of (PAEK-2) are repeating units (J'-P) is there. More preferably, at least 95 mol% of the repeating units of PAEK-2 are repeating units (J'-P). Most preferably, all of the repeating units of PAEK-2 are repeating units (J'-P). This PAEK-2 can be produced by a polycondensation reaction between bisphenol A and 4,4'-dihalodibenzophenone, typically 4,4'-difluorodibenzophenone, according to a known method.

  In still another preferred embodiment of the present invention, at least 50 mol% of the repeating units of (PAEK-2) are a combination of repeating units (J′-A) and (J ″ -A). Preferably at least 60 mol%, preferably at least 70 mol%, even more preferably at least 80 mol%, most preferably at least 90 mol% of the repeating units of (PAEK-2) are repeating units (J'-A) And (J ″ -A). More preferably, at least 95 mol% of the repeating units of (PAEK-2) are the repeating units (J′-A) and (J ″ -A). Most preferably, all of the repeating units of (PAEK-2) are repeating units (J′-A) and (J ″ -A).

  In still another preferred embodiment of the present invention, at least 50 mol% of the repeating units of (PAEK-2) are repeating units (J ″ -A). Preferably at least 60 mol%, preferably at least 70 mol%, even more preferably at least 80 mol%, most preferably at least 90 mol% of the repeating units of (PAEK-2) are repeating units (J ″ -A ). More preferably, at least 95 mol% of the repeating unit of (PAEK-2) is the repeating unit (J ″ -A). Most preferably, all of the repeating units of (PAEK-2) are repeating units (J ″ -A).

  In still another preferred embodiment of the present invention, at least 50 mol% of the repeating units of (PAEK-2) are repeating units (J ″ -Q). Preferably, at least 60 mol%, preferably at least 70 mol%, even more preferably at least 80 mol%, most preferably at least 90 mol% of the repeating units of (PAEK-2) are repeating units (J ″ -Q ). More preferably, at least 95 mol% of the repeating units of (PAEK-2) are repeating units (J ″ -Q). Most preferably, all of the repeating units of (PAEK-2) are repeating units (J ″ -Q).

Preferably, (PAEK-2) is at least 0.03 kN-s / m ² measured according to ASTM D3835 at 400 ° C. and 1000 s ⁻¹ using a 0.5 × 3.175 mm tungsten carbide die. preferably at least 0.04kN-s / ^{m 2,} more preferably shows a melt viscosity of at least 0.05kNs / ^{m 2.}

Preferably, (PAEK-2) is measured according to ASTM D3835 at 400 ° C. and 1000 s ⁻¹ using a 0.5 × 3.175 mm tungsten carbide die, at most 0.65 kN-s / m ² , more preferably at most 0.60kN-s / ^{m 2,} more preferably at most 0.50kN-s / ^{m 2.} The melt viscosity of is shown.

  Preferably, (PAEK-2) is at least 0.2 dL / g, more preferably at least 0.3 dL / g, most preferably at 0.1% in concentrated sulfuric acid at 25 ° C. measured according to ASTM D2857-95 Exhibits an intrinsic viscosity of at least 0.4 dL / g.

  Preferably, (PAEK-2) is measured at 0.1% in concentrated sulfuric acid at 25 ° C., at most 2.0 dL / g, more preferably at most 1.7 dLg /, most preferably at most 1. An intrinsic viscosity of 5 dL / g is shown.

Preferably, (PAEK-2) is a temperature (“T _d ”) greater than about 300 ° C., greater than about 350 ° C., or greater than about 400 ° C. as measured by thermogravimetric analysis (“TGA”) according to ASTM D3850 standard. Shows a 5% weight loss. TGA measurements are performed under a nitrogen atmosphere using a starting temperature of 30 ° C., an end temperature of 800 ° C., a heating rate of 10 ° C./min, and a flow rate of 60 mL / min.

Blend (B) of (PAEK-1) and (PAEK-2)
For purposes of the present invention, (PAEK-1) and (PAEK-2) are blended together to provide blend (B) according to methods known in the art. Although multiple (PAEK-1) and multiple (PAEK-2) can be used in blend (B), blend (B) is preferably one (PAEK-) in combination with one (PAEK-2) 1) only. As used herein, the term “blend” is intended to mean a homogeneous (or uniform) physical mixture of two polymers. The blend can be obtained by any method known in the art that is a convection-dominated mixing motion, including melt mixing (or melt blending), solution blending and latex mixing.

  Advantageously, blend (B) is produced by melt blending, as described in detail below with respect to composition (C).

  Alternatively, blend (B) can be made by powder blending, as described in detail below with respect to composition (C).

  (PAEK-1) and (PAEK-2) are mixed in various weight ratios, provided that the weight of (PAEK-1) is higher than the weight of (PAEK-2), ie (PAEK-1) ) Contains more than 50% by weight of blend (B). Advantageously, (PAEK-1) comprises at least 60% by weight of blend (B), preferably at least 70% by weight of blend (B), more preferably at least 75% by weight of blend (B). In some cases, (PAEK-1) comprises at least 90% by weight of blend (B).

Advantageously, method (M) is carried out using blend (B-1), which method comprises:
-PEEK in which at least 98 mol% of the repeating units are units of formula (J'-A) (PAEK-1);
-At least 50 mol% of the repeating unit is a combination of units of formula (J'-B) and (J "-B), a combination of units of formula (J'-A) and (J'-D), a formula (PAEK-2) which is a unit of (J ′ ″-A), a unit of formula (J′-P), or a combination of units of formula (J′-A) and (J ″ -A); including.

Preferred examples of the blend (B-1) are
1)-PEEK whose at least 98 mol% repeat units are units of formula (J'-A) (PAEK-1);
A blend (B-1a) comprising (PAEK-2) PEKK, wherein at least 95 mol% of the repeating units are units of formulas (J′-B) and (J ″ -B).
2) —PEEK in which at least 98 mol% of the repeating units are units of formula (J′-A) (PAEK-1);
A blend (B-1b) comprising PEEK-PEDEK (PAEK-2) wherein at least 95 mol% of the repeating units are repeating units (J′-A) and (J′-D).
3)-PEEK in which at least 95 mol% of the repeating units are units of the formula (J'-A) (PAEK-1);
-A blend (B-1c) comprising (PAEK-2) wherein at least 95 mol% of the repeating units are repeating units (J'-P) (PAEK-2),
4)-at least 98 mol% of PEEK is a unit of formula (J'-A) (PAEK-1)
-At least 50 mol% of the repeating unit is a repeating unit (J '''-A), and the remainder of the repeating unit is a sulfonated PEEK (PAEK-2) which is a unit (J'-A). Blend (B-1d),
5)-PEEK in which at least 98 mol% of the repeating units are units of the formula (J'-A) (PAEK-1);
A blend (B-1e) comprising (PAEK-2), which is PAEK in which at least 95% of the repeating units are repeating units (J′-A) and (J ″ -A).

  Advantageously, the blend is blend (B-1a) or blend (B-1b).

In a further embodiment, method (M) advantageously comprises:
The aforementioned (PAEK-1), preferably at least 50 mol% of the repeating units are of the formula (J′-A), the combination of units (J′-B) and (J ″ -B), or the formula (J According to '-C), (PAEK-1),
-Implemented in a blend (B-2) comprising (PAEK-2) as described above, wherein at least 50% of the repeating units are according to formula (J "-A) or (J" -Q).

Advantageously, method (M) comprises
1)-PEEK whose at least 98 mol% repeat units are units of formula (J'-A) (PAEK-1);
-At least 95 mol% of repeating units, preferably PAEK which is a repeating unit (J ″ -A) [hereinafter also referred to as (PEmEK)] (PAEK-2). Blend (B-2a),
2) —PEEK in which at least 98 mol% of the repeating units are units of formula (J′-A) (PAEK-1);
-At least 95 mol% of repeating units, preferably all repeating units are PAEK (PAEK-2) which is a repeating unit (J ″ -Q) [hereinafter also referred to as (PEDEKmK)]. Implemented in blend (B-2b).

  More advantageously, method (M) is carried out with blend (B2-b).

Blend (B-1) where (PAEK-2) is not PEEK-PEDEK represents a further aspect of the present invention. An advantageous example of such a blend is
-PEEK in which at least 98 mol% of the repeating units are units of formula (J'-A) (PAEK-1);
-At least 50 mol% of the repeating unit is a combination of units of formula (J'-B) and (J "-B), unit of formula (J"'-A), of formula (J'-P) (PAEK-2) which is a unit or a combination of units of the formulas (J′-A) and (J ″ -A). Preferred examples of such a blend are the aforementioned blends (B1-a), (B1-c), (B1-d), and (B1-e), with the blend (B1-a) being preferred.

  Blend (B-2) represents a further aspect of the present invention, and blends (B-2a) and (B2-b) are preferred, and blend (B2-b) is more preferred.

Composition (C) exhibits good chemical resistance, preferably at least 19 J / g polymer (excluding any components detailed below), more preferably at least 26 J / g polymer, More preferably, the melting enthalpy is measured by 2 ^nd thermal DSC scanning of at least 32 J / g polymer, more preferably at least 39 J / g polymer, most preferably at least 43 J / g polymer.

  Composition (C) exhibits good chemical resistance demonstrated in environmental stress cracking resistance (ESCR) experiments conducted as described in detail in the experimental section below. Preferably, composition (C) exhibits a critical strain for breakage of at least 0.5% after 24 hours immersion exposure with toluene or methyl ethyl ketone at room temperature. More preferably, composition (C) exhibits a critical strain for failure of at least 0.7%, most preferably at least 0.9% after this exposure.

Optional components in composition (C) The composition (C) for carrying out the method (M) can consist of only the aforementioned blend (B) or contain further components, in particular reinforcing fillers. Can be included. In one embodiment, composition (C) comprises, preferably consists of the aforementioned blend (B) and at least one reinforcing filler.

  Many different reinforcing fillers can be included in the composition (C). Preferably these are selected from fibrous and particulate fillers. For the purposes of the present invention, fibrous reinforcing filler is a material having a length, width and thickness, with the average length being significantly greater than both width and thickness. In general, such materials have an aspect ratio, defined as an average ratio between length and maximum width and thickness of at least 5. Preferably, the aspect ratio of the reinforcing filler is at least 10, more preferably at least 20, even more preferably at least 50.

  More preferably, the reinforcing filler is a mineral filler (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate), glass fiber, carbon fiber, synthetic polymer fiber, aramid fiber, aluminum fiber, titanium fiber. , Magnesium fiber, boron carbide fiber, rock wool fiber, steel fiber, wollastonite and the like. Even more preferably, it is selected from mica, kaolin, calcium silicate, magnesium carbonate.

  In one embodiment, the filler is selected from fibrous fillers.

  Advantageously, the reinforcing filler is selected from glass fibers and carbon fibers. Excellent results have been obtained when glass fibers are used. Glass fibers are silica-based glass compounds that contain several metal oxides that can be tuned to produce different types of glasses. The main oxide is silica in the form of silica sand, and other oxides such as calcium, sodium, and aluminum are incorporated to lower the melting temperature and prevent crystallization. The glass fibers can have a circular or non-circular cross-section (so-called “flat glass fibers”), including oval, elliptical, or rectangular. Glass fibers can be added as endless fibers, chopped glass fibers or milled glass fibers, with chopped glass fibers being preferred. The glass fibers generally have an equivalent diameter of 5-20 mm, preferably 5-15 mm, more preferably 5-10 mm. A, C, D, E, M, S, R, T glass fibers (described in 5.2.3 of Additives for Plastics Handbook, 2nd ed, John Murphy, pages 43-48), or any of these All glass fiber types, such as mixtures of these, or mixtures thereof, can be used, but E and S glass fibers are preferred.

  In a further embodiment, the filler is a granular filler. Examples of particulate fillers are zinc oxide, zinc sulfide, mica, silica, talc, alumina, kaolin, calcium sulfate, calcium carbonate, titanium oxide, clay, glass powder, nickel carbonate, iron oxide, quartz powder, magnesium carbonate, fluorine Resins, barium sulfate, graphite, carbon powder, and nanotubes. Non-fibrous fillers can be introduced in the form of a powder or in the form of flaky particles.

  In another preferred embodiment, composition (C) comprises at least one fibrous reinforcing filler and at least one granular reinforcing filler.

  In the polymer composition (C), at least one reinforcing filler is advantageously at least 5% by weight, preferably at least 10% by weight, more preferably at least 15% by weight, based on the total weight of the polymer composition (C). %, Even more preferably at least 20% by weight, even more preferably at least 25% by weight, even more preferably at least 26% by weight, and most preferably at least 28% by weight.

  The reinforcing filler is also advantageously at most 50% by weight, preferably at most 45% by weight, more preferably at most 40% by weight, even more preferably, based on the total weight of the polymer composition (C). It is present in an amount of at most 35 wt%, even more preferably at most 34 wt%, most preferably at most 32 wt%.

  Preferably, the reinforcing filler is 20 to 50 wt%, more preferably 25 to 45 wt%, even more preferably 26 to 40 wt%, most preferably 28, based on the total weight of the polymer composition (C). Present in an amount in the range of ˜34% by weight.

  Composition (C) comprises a further polymer selected from polyarylethersulfone (PAES), polyphenylene sulfide (PPS), and polyetherimide (PEI), or mixtures thereof, (PAEK-1) and (PAEK). -2) in an amount of 50% by weight or less based on the total weight, and may further be included.

  The polymer composition (C) may further comprise UV stabilizers, heat stabilizers, antioxidants, pigments, processing aids, lubricants, flame retardants, and / or conductive additives such as carbon black and carbon nanofibrils. Can optionally further comprise an additive.

  In a preferred embodiment, composition (C) does not contain ferromagnetic or ferromagnetic conductive particles.

  In a further preferred embodiment, the composition does not contain more than 0.5% by weight of low molecular weight aromatic compounds. Preferably, it does not contain more than 0.5% by weight of aromatic compounds having a molecular weight of up to 3,000 g / mol.

Advantageously, the composition (C) is
-Blend (B-1) or (B-2), and-comprising glass fiber, preferably consisting of these.

More advantageously, the composition (C) is
-Blend (B-1a), (B-1b), (B-2a) or (B-2b), and glass fiber.

Production of composition (C) and its use Composition (C) can be produced by any known melt mixing process suitable for preparing thermoplastic compositions. Such a process is typically carried out by heating (PAEK-1) and (PAEK-2) at least above the melting temperature of PAEK-1 (which is the highest melt component of the blend), thereby Form blend (B) in molten form and then extrude pelletize. The process can be carried out in a melt mixing apparatus, for which any melt mixing apparatus known to those skilled in the art that prepares the polymer composition by melt mixing can be used. Suitable melt mixing equipment is, for example, a kneader, a Banbury mixer, a single screw extruder, a twin screw extruder. Preferably, an extruder is used that is equipped with means for charging all of the desired components into the extruder, the feed port or melt of the extruder. In the process for the preparation of the polymer composition (C), the components for forming the composition are fed to a melt mixing device and melt mixed in that device. The components can be supplied simultaneously as a powder or granule mixture, also known as a dry blend, or can be supplied separately.

  Advantageously, if composition (C) comprises one or more optional ingredients, such ingredients are added to and mixed with melt blend (B) and if two or more additional ingredients are used, Such ingredients are preferably premixed before being added to the melt (B).

  Alternatively, composition (C) can be produced by powder blending. Such a process is typically carried out by mixing (PAEK-1) and (PAEK-2) fine powders (at least 90% pass through a fine screen of 150 μm or less) in the desired amount. The This process can be carried out in a solid or fine powder mixer. Mixer types that can be used for this purpose include tumble type mixers, ribbon type mixers, impeller type mixers, also known as high intensity mixers, shaker type mixers, and other types of solids known in the art. And a powder mixer.

The composition (C) is thus obtained in the form of pellets or powder which are subsequently processed into the final article [article (A)]. It will be apparent to those skilled in the art that composition (C) must be heated to a temperature above the melting temperature of PAEK-1 before being processed into a final article.
Preferably, composition (C) is used in method (M) to produce a coating for a metal surface.

  However, because of the combination of toughness, ductility, chemical resistance, and high temperature performance, the composition (C) can also be used in 3D printing (additional manufacturing) such as melt filament processing (FFF) or selective laser sintering (SLS). Can also be used in processing technology (also known as). A commercially available 3D printing processing facility of the FFF type is, for example, Stratasys, Inc. And manufactured under the trademark of Fortus®. Examples of SLS-based 3D printing devices are available from EOS Corporation, such as those sold under the trademark EOSINT®. Composition (C) can also be used to make stock shapes that can be used for subsequent machining into final parts. The stock shape can be in the form of a rod, slab, sheet, tube, billet, or other three-dimensional shape suitable for further machining into the final article. Stock shapes can be made by extrusion, injection molding, or compression molding, as well as other polymer melt processing techniques known in the art.

Article (A ′) comprising a metal surface coated with composition (C) and the aforementioned surface
The coated metal surface (S) according to the invention is produced by a method (M) comprising the step of applying a composition (C) to the metal surface. The metal surface can have any shape, i.e. it can be a two-dimensional (or planar) surface or a three-dimensional surface. Part or all of the metal surface can be covered with the composition (C).

  Conveniently, the metal surface comprises aluminum and / or copper or steel.

  The metal surface can be, for example, the surface of a wire, such as an electric wire or cable, or the surface of an electronic device, particularly a structural part of an electronic device for mobile communication. Non-limiting examples of devices for mobile communications are laptops, cell phones, GPS, tablets, personal digital assistants, portable recording devices, portable playback devices, and portable radio receivers.

  Typically, composition (C) is overmolded over the metal surface. Conveniently, the pellet of composition (C) is melted above its melting temperature to form a molten composition (C), which is brought into contact with the surface of the metal article. Contact is preferably made in an injection mold.

  Alternatively, the composition (C) is applied to the metal surface by powder coating or slurry coating.

  Prior to contacting the composition (C) with the metal surface, the surface is removed to remove contaminants and / or grease and / or to chemically modify the surface and / or to change the surface profile. To be processed appropriately. Examples of treatments include surface abrasion to roughen the surface, addition of adhesion promoters, chemical etching, functionalization of the surface by exposure to plasma and / or radiation (eg laser or UV irradiation), or these Any combination of Preferably, the metal surface is published in European Patent Application No. 1459882A (Taisei Plas Co., Ltd.) published August 7, 2003 and European Patent Application Publication No. 1559542A published on August 3, 2005. A chemically nano-etched metal surface as described in the document (Taisei Plas Co., Ltd.) (so-called nano-forming technique or NMT treatment)

  The electronic device structural components resulting from the foregoing method are typically assembled with other components to produce an electronic device, particularly a mobile electronic device.

  Articles (A ') comprising a surface that is at least partially coated according to the method (M) of the present invention are a further object of the present invention. In particular, the article (A ′) is selected from wires such as electric wires or cables, or structural parts of electronic devices, in particular electronic devices for mobile communication. Non-limiting examples of devices for mobile communications are laptops, cell phones, GPS, tablets, personal digital assistants, portable recording devices, portable playback devices, and portable radio receivers.

  The metal surface composition assembly preferably exhibits a lap shear strength of at least 10 MPa or 1450 psi as measured by ASTM D1002.

  The invention will be described herein below in more detail in the following experimental section.

  In the event that the disclosure of any patent, patent application, and publication incorporated by reference into this specification contradicts the description of this application to the extent that the term may be obscured, this description shall control.

Experimental Items Raw Materials KESTASPIR (registered trademark) KT-880 NL [MV (400 ° C., 1000 s ⁻¹ )] is 0.15 kPa · s, T _m = 344 ° C.], KESPISPI® KT-880P [MV (400 ° C.) , 1000 s-1) is 0.15 kPa. s, T _m = 344 ° C.], KESPIIR® KT-890 NL [MV (400 ° C., 1000 s ⁻¹ )] is 0.09 kPa. _{s, T m = 345 ℃]} , and KETASPIRE (TM) KT-820FP [MV (400 ℃, 1000s-1) is 0.40 kPa. s, T _m = 340 ° C.] is an aromatic polyetheretherketone (PEEK) polymer available from Solvay Specialty Polymers USA, LLC. Cypek® DS-E and DS-M PEKK are amorphous polyetherketone ketones (PEKK) available from Cytec. Cypek® DS-E and DS-M PEKK contain repeating units (J′-B) and (J ″ -B) in a molar ratio of 55/45 to 65/35. The “Td 5% loss” of the DS-E polymer is 542 ° C.

  Cypek® FC PEKK is a crystalline polyether ketone ketone (PEKK) available from Cytec. Cypek® FC PEKK contains repeating units (J′-B) and (J ″ -B) in a molar ratio of 66/34 to 75/25. 4,4'-biphenol and polymer grade were procured from SI, USA. 1,3-bis (4'-fluorobenzoyl) benzene, 99% is a product of 3B Scientific Corp. , IL, USA and purified by recrystallization from monochlorobenzene before use to reach a final purity of 99 +% by HPLC. Resorcinol, a technical grade, was procured from Indspec, USA. 4,4'-Difluorobenzophenone, polymer grade, was procured from Jintan, China. Diphenylsulfone (polymer grade) was procured from Proviron (99.8% purity). Sodium carbonate and light soda ash are Solvay S. A. , From France. Potassium carbonate with d90 <45 μm was procured from Armand products. Lithium chloride (anhydrous grade) was procured from Acros.

  Fiber glass: Chopped E type glass fiber OCV910A was procured from Owens Corning.

Determining a melting temperature _{T m} of a melting temperature, ASTM D3418-03, E1356-03, E793-06, by E794-06, was determined as the peak temperature of the melting endotherm at ^{2 nd} heat scan of a differential scanning calorimeter (DSC) . Details of the procedure used in the present invention are as follows: TA Instruments DSC Q20 was used as carrier gas with nitrogen (purity 99.998%, 50 mL / min). Calibration of temperature and heat flow was performed using indium. The sample size was 5-7 mg. The weight was recorded as ± 0.01 mg. Thermal cycle is
-First thermal cycle: 30.00 ° C to 400.00 ° C at 20.00 ° C / min, isothermal at 400.00 ° C for 1 minute,
-1st cooling cycle: 400.00 ° C to 30.00 ° C at 20.00 ° C / min, isothermal for 1 minute,
Second heat cycle: 30.00 ° C. to 400.00 ° C. at 20.00 ° C./min, isothermal at 400.00 ° C. for 1 minute.
Melting temperature T _m is determined as the peak temperature of the melting endotherm in the second heat scan. The melting enthalpy was determined in the second thermal scan. The melting of the composition was taken as the area over a linear baseline drawn from 220 ° C. to a temperature above the final endotherm (typically 370-380 ° C.).

Determination of the melting enthalpy The melting enthalpy is determined according to ASTM D3418-03, E1356-03, E793-06, E794-06 with a second heat in a differential scanning calorimeter (DSC) using a heating and cooling rate of 20 ° C./min. It is determined as the area under melting endotherm in the scan. The melting enthalpy is determined in the second thermal scan and is taken as the area over a linear baseline drawn from above Tg to a temperature above the endothermic end point.

  For a filled composition, the measured melting enthalpy corrects for the filler content and represents the melting enthalpy for only the polymer content excluding the filler.

Environmental stress cracking resistance (ESCR)
The environmental stress cracking resistance was evaluated by immersing a bending bar attached to a parabolic fixture having a curvature radius that continuously changed and a strain of 0 to 2.0%. The test was conducted in an organic solvent such as toluene and methyl ethyl ketone. Failure is defined as cracking or cracking at or below the exposed bar surface, even if minor. A failure is also considered to have occurred if the material shows any signs of solvent swelling, softening, or solvation at any strain level. The test was conducted with an ASTM flex bar, 5 inches long, 0.5 inches wide, and 0.125 inches thick, annealed at 200 ° C. for 2 hours.

Synthesis Examples Example 1 - Poly (ether bisphenol A ketone) [recurring units (J'-P)] Synthesis stirrer, _{N 2} inlet tube, Claisen adapter with placed in the reaction medium thermocouple and condenser and, To a 1 L 4-neck reaction flask equipped with a Dean-Stark trap with a dry eye strap, 169.70 g N, N-dimethylacetamide, 254.5 g toluene, 111.93 g bisphenol A (0.490 mol), 84.70 g of dry potassium carbonate (0.613 mol) was introduced. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O ₂ ). This operation was repeated twice. The reaction mixture was then placed under a constant nitrogen purge (60 mL / min).

The reaction mixture was slowly heated to 130 ° C. The azeotrope toluene / water was collected and the water was separated. The reaction mixture was held at 130 ° C. for 4 hours while removing water with the azeotrope. At 130 ° C., a solution of 107.63 g of 4,4′-difluorodibenzophenone (0.493 mol) dissolved in 169.70 g of N, N-dimethylacetamide was added to the reaction mixture by addition funnel over 30 minutes. Added. At the end of the addition, the reaction mixture was heated to 165 ° C. After 40 minutes at 165 ° C., 4.279 g of 4,4′-difluorodibenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 15 minutes, 20.78 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 3.2095 of 4,4′-difluorodibenzophenone was added to the reactor and the reaction mixture was held at temperature for 30 minutes. The reactor contents were then coagulated in 2.0 L of methanol. The solid was filtered and washed with the mixture acetone / methanol (50/50) and then with water at a pH of 1-12. The final wash water had a pH of 6-7. The powder was then dried at 120 ° C. under vacuum for 12 hours to produce 171.3 g of white powder. Analysis by SEC showed that the polymer had Mn = 34046, Mw = 123149. DSC showed the polymer to be amorphous with a Tg (half height) of 157 ° C. The glass transition temperature Tg and the melting temperature _Tm are specified in accordance with ASTM D3418, as detailed above and, accordingly, from the second thermal scan on the differential scanning calorimeter, 20 ° C./min from 30 ° C. to 400 ° C. The heating rate was determined.

  Size exclusion chromatography (SEC) was performed using methylene chloride as the mobile phase. Two 5 micron (“μm”) mixed D SEC columns (Agilent Technologies) with guard columns were used for the separation. A 254 nm UV detector was used to obtain the chromatogram. A flow rate of 1.5 mL / min and an injection volume of 20 microliters (“μL”) of 0.2 wt% / volume (“w / v”) solution in the mobile phase were selected. Calibration was performed using narrow calibration standards polystyrene (Agilent Technologies) (calibration curve: 1) type: relative, narrow calibration standard calibration 2) fit: cubic regression). Data were acquired, calibrated, and molecular weights measured using Empower Pro GPC software (Waters).

  The “Td 5% loss” of the polymer was 498 ° C. “Td 5% loss” refers to the average temperature at which 5% of the weight of the material has been lost as determined by thermogravimetric analysis (“TGA”) according to the ASTM D3850 standard. TGA was performed on a TA Instruments TGA Q500 from 30 ° C. to 800 ° C. under nitrogen (60 mL / min) at 10 ° C./min.

Example 2-Synthesis of sulfonated PEEK [repeat units (J'-A) and (J '''-A)] This example demonstrates the synthesis of H + and Na + forms for sulfonated PEEK.

In order to demonstrate the synthesis of the sulfonated PEEK H ⁺ form, it is equipped with a stirrer, N ₂ injection tube, Claisen adapter with thermocouple in the reaction medium, and a Dean-Stark trap with condenser and dry eye strap Into a 3 L 4-neck reaction flask was introduced 2.0 L concentrated H ₂ SO ₄ (96%) and 300.00 g KT820FP powder (commercially available from Solvay Specialty Polymers USA, LLC). At the end of the addition, the reaction mixture was heated to 50 ° C. with stirring and under a nitrogen atmosphere. The mixture was held at 50 ° C. for 6 hours and then coagulated under high shear (Waring blender) in 24 L of demineralized water. The solid was filtered and washed with water and aqueous Na ₂ CO ₃ until the pH was higher than 7. The solid was then dried at 100 ° C. under vacuum for 12 hours to produce 578 g of a soft hygroscopic solid. Analysis by FTIR is described in Xigao et al., Incorporated herein by reference. Brit. It was shown to be identical to the sulfonated PEEK described in Polymer Journal, 1985, V17, P4-10.

DSC showed the polymer to be amorphous with a Tg of 108 ° C. (half height). The “Td 5% loss” of the polymer was 452 ° C. Elemental analysis of sulfur showed that the polymer was 51% sulfonated. The synthesized copolymer was represented by the following formula.

Example 3 Preparation of PEEK-PEDEK Copolymer 70/30 [Repeating Units (J′-A) and (J′-D)] A Claisen Adapter with Stirrer, N ₂ Injection Tube, Thermocouple Placed in Reaction Medium , And a 500 mL 4-neck reaction flask equipped with a condenser and a Dean-Stark trap with dry eye strap, 129.80 g diphenylsulfone, 18.942 g hydroquinone, 13.686 g 4,4 ′ biphenol, and 54 .368 g of 4,4′-difluorobenzophenone was introduced. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O ₂ ). The reaction mixture was then placed under a constant nitrogen purge (60 mL / min).

The reaction mixture was slowly heated to 150 ° C. At 150 ° C., a mixture of 26.876 g Na ₂ CO ₃ and 0.1524 g K ₂ CO ₃ was added to the reaction mixture via a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 ° C. at 1 ° C./min. After 10 minutes at 320 ° C., 6.415 g of 4,4′-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.418 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 2.138 g of 4,4′-difluorobenzophenone was added to the reactor and the reaction mixture was held at temperature for 15 minutes.

The reactor contents were then poured from the reactor into the SS pan and cooled. The solid was crushed and ground with an attrition mill through a 2 mm screen. Diphenyl sulfone and salt were extracted from the mixture with acetone and water at a pH of 1-12. The powder was then removed from the reactor and dried under vacuum at 120 ° C. for 12 hours to obtain 73 g of white powder. Polymer repeat units are:
It is.
The melt viscosity measured by capillary rheology at 400 ° C. and 1000 s−1 using a 0.5 × 3.175 mm tungsten carbide die was 0.19 kN−s / m ² . The “Td 5% loss” of the polymer was 561 ° C.

Example 4: Preparation of PEEK-PEDEK Copolymer 75/25 [Repeating Units (J′-A) and (J′-D)] Claisen Adapter with Stirrer, N ₂ Injection Tube, Thermocouple Placed in Reaction Medium , And a 500 mL 4-neck reaction flask equipped with a Dean-Stark trap with a condenser and dry eye strap, was charged with 128.21 g diphenyl sulfone, 20.295 g hydroquinone, 11.405 g 4,4 ′ biphenol, and 54 .368 g of 4,4′-difluorobenzophenone was introduced. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O ₂ ). The reaction mixture was then placed under a constant nitrogen purge (60 mL / min).

The reaction mixture was slowly heated to 150 ° C. At 150 ° C., a mixture of 26.876 g Na ₂ CO ₃ and 0.169 g K ₂ CO ₃ was added to the reaction mixture via a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 ° C. at 1 ° C./min. After 10 minutes at 320 ° C., 6.415 g of 4,4′-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.418 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 2.138 g of 4,4′-difluorobenzophenone was added to the reactor and the reaction mixture was held at temperature for 15 minutes.

  The reactor contents were then poured from the reactor into the SS pan and cooled. The solid was crushed and ground with an attrition mill through a 2 mm screen. Diphenyl sulfone and salt were extracted from the mixture with acetone and water at a pH of 1-12. The powder was then removed from the reactor and dried under vacuum at 120 ° C. for 12 hours to obtain 74 g of white powder.

Polymer repeat units are:
It is.

The melt viscosity measured by capillary rheology at 400 ° C. and 1000 s−1 using a 0.5 × 3.175 mm tungsten carbide die was 0.15 kN−s / m ² . The “Td 5% loss” of the polymer was 557 ° C.

Example 5: PEEK-PEDEK copolymer 80/20 [recurring units (J'-A) and (J'-D)] Claisen adapter with preparation stirrer, _{N 2} inlet tube, charged was a thermocouple in the reaction medium , And a 500 mL 4-neck reaction flask equipped with a Dean-Stark trap with a condenser and a dry-eye strap, 127.7 g diphenyl sulfone, 21.861 g hydroquinone, 9.207 g 4,4 ′ biphenol, and 54 .835 g of 4,4′-difluorobenzophenone was introduced. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O ₂ ). The reaction mixture was then placed under a constant nitrogen purge (60 mL / min).

The reaction mixture was slowly heated to 150 ° C. At 150 ° C., a mixture of 27.339 g Na ₂ CO ₃ and 0.171 g K ₂ CO ₃ was added to the reaction mixture via a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 ° C. at 1 ° C./min. After 4 minutes at 320 ° C., 6.577 g of 4,4′-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 1.285 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 2.192 g of 4,4′-difluorobenzophenone was added to the reactor and the reaction mixture was held at temperature for 15 minutes.

  The reactor contents were then poured from the reactor into the SS pan and cooled. The solid was crushed and ground with an attrition mill through a 2 mm screen. Diphenyl sulfone and salt were extracted from the mixture with acetone and water at a pH of 1-12. The powder was then removed from the reactor and dried under vacuum at 120 ° C. for 12 hours to obtain 72 g of white powder.

Polymer repeat units are:
It is.
The melt viscosity measured by capillary rheology at 400 ° C. and 1000 s−1 using a 0.5 × 3.175 mm tungsten carbide die was 0.20 kN-s / m ² . The “Td 5% loss” of the polymer was 561 ° C.

Example 6: Preparation of PEmEK polymer [repeat unit (J ″ -A)] Stirrer, N ₂ inlet tube, Claisen adapter with thermocouple placed in reaction medium, and Dean with condenser and dry eye strap -A 500 mL 4-neck reaction flask equipped with a Stark trap was charged with 128.63 g diphenyl sulfone, 28.853 g resorcinol, and 58.655 g 4,4'-difluorobenzophenone. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O ₂ ). The reaction mixture was then placed under a constant nitrogen purge (60 mL / min).

The reaction mixture was slowly heated to 150 ° C. At 150 ° C., a mixture of 28.742 g Na ₂ CO ₃ and 0.182 g K ₂ CO ₃ was added to the reaction mixture via a powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 275 ° C. at 1 ° C./min. After 1 minute at 275 ° C., 6.860 g of 4,4′-difluorobenzophenone was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.447 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 2.287 g of 4,4′-difluorobenzophenone was added to the reactor and the reaction mixture was held at temperature for 15 minutes.

The reactor contents were then poured from the reactor into a stainless steel pan and cooled. The solid was crushed and ground with an attrition mill through a 2 mm screen. Diphenyl sulfone and salt were extracted from the mixture with acetone and water at a pH of 1-12. The powder was then removed from the reactor and dried under vacuum at 120 ° C. for 12 hours to obtain 67 g of a light brown powder. The repeat unit of the polymer is 100% (J ″ -A).

  The melt viscosity measured by capillary rheology at 410 ° C. and 46 s-1 according to ASTM 3835 was 0.33 kN-s / m 2.

  DSC revealed that the polymer was amorphous with a Tg of 122 ° C.

Example 7: PEDEKmK polymer [recurring units (J '' - Q)] Preparation stirrer, _{N 2} inlet tube, Claisen adapter with thermocouple placed in the reaction medium, as well as the condenser and Dean with dry ice trap A 500 mL 4-neck reaction flask equipped with a Stark trap was charged with 128.44 g diphenylsulfone, 29.980 g 4,4 ′ biphenol, and 53.188 g 1,3-bis (4′-fluorobenzoyl) benzene. Introduced. The flask contents were evacuated under vacuum and then filled with high purity nitrogen (containing less than 10 ppm O2). The reaction mixture was then placed under a constant nitrogen purge (60 mL / min).

The reaction mixture was slowly heated to 150 ° C. At 150 ° C., a mixture of 17.662 g Na ₂ CO ₃ and 0.111 g K ₂ CO ₃ was added to the reaction mixture by powder dispenser over 30 minutes. At the end of the addition, the reaction mixture was heated to 320 ° C. at 1 ° C./min. After 1 minute at 275 ° C., 2.076 g of 1,3-bis (4′-fluorobenzoyl) benzene was added to the reaction mixture while maintaining a nitrogen purge in the reactor. After 5 minutes, 0.550 g of lithium chloride was added to the reaction mixture. After 10 minutes, another 1.038 g of 1,3-bis (4′-fluorobenzoyl) benzene was added to the reactor and the reaction mixture was held at temperature for 15 minutes.

The reactor contents were then poured from the reactor into a stainless steel pan and cooled. The solid was crushed and ground with an attrition mill through a 2 mm screen. Diphenyl sulfone and salt were extracted from the mixture with acetone and water at a pH of 1-12. The powder was then removed from the reactor and dried under vacuum at 120 ° C. for 12 hours to obtain 69 g of white powder. The repeat unit of the polymer is 100% (J ″ -Q).

The melt viscosity as measured by capillary rheology at 410 ° C. and 46 s ⁻¹ according to ASTM 3835 was 0.23 kN-s / m 2.

DSC showed the polymer to exhibit a T _m of 306 ° C.

General Description of Formulation Process for Polymer Blend Preparation and Production of Test Raw Material Only Polymer Blend In Table 1, the raw material only polymer blend consisting of PEEK as PAEK-1 and PEAK-2 is either Coperion® ZSK26 or Berstorff It was prepared by melt blending with a simultaneous rotating meshing twin screw extruder. The blending conditions for each machine used a barrel temperature set point of 340-350 ^° C.

  For the PEEK / PAEK-2 blend, the specimens had a temperature profile of the zone at the rear of 349-354 ° C, the middle of 371-377 ° C, and the front of 377-390 ° C with a molding temperature of 150-200 ° C. Was molded.

Results and Discussion The raw material only (ie, no additional components) blends of PEEK and PEEK-PEDEK [Blend (B-1b) in the description] having the composition shown in Table 1a show performance advantages over raw material only PEEK. (Table 1). The PEEK / PEEK-PEDEK blend exhibits high fluidity as shown in Examples E5 and E6, similar to Ketasire® KT-890 PEEK (Comparative Example C1). The PEEK / PEEK-PEDEK elastic modulus and strength are similar to those of PEEK with only the raw material (Comparative Example C1), but exhibit higher ductility due to the tensile strain at break as compared with PEEK with only the raw material. Furthermore, the notched impact and dynaup impact performance demonstrated similar or better performance compared to raw material-only PEEK. The improved performance in Dynatap failure mode, where the number of brittle vs. ductile failure modes is noted, is only 25% PAEK-2 blended with PEEK, the performance of the blend against 100% ductile failure mode in the Dynatap test. This is particularly improved in Example E5 in which Similar performance was observed in composition (C) comprising a blend of PEEK / PEEK-PEDEK and glass fibers as reinforcing fibers and the results are shown in Table 2. This result shows that when PEEK-PEDEK is used as PAEK-2, the flowability, elastic modulus, and strength of the control composition containing only PEEK-PEDEK and glass fibers (controls C12-C14) are improved. Yes. This data also shows the tensile elongation at break of Examples E8-E11 compared to a control composition comprising PEEK and glass fiber (Comparative Example C7), and the improved ductility due to the superior notched impact of such a control composition. . The notched Izod performance was improved, but the tensile strength and tensile modulus showed the same performance as PEEK, Comparative Example C7.

Examples C15 and E16-Improved Adhesion in Chemically Nano-etched Metal Substrates The following example is compared to prior art compositions, published European Patent Application No. 1459882A1, assigned to Taiseiplus corporation. Obtained from the overmold composition of the present invention on chemically nano-etched metal surfaces as described in the specification and EP 1559542 A1 (so-called nano-molding technology or NMT treatment) Illustrates improved adhesion.

Blending and Formulation In Example E16 of Table 3, the two polymer components of the composition (PAEK-1, PAEK-2) were first tumbled on a 5 gallon drum for 20 minutes to make a resin premix. . The premix was then weighed into the feed port of a 25 mm Berstorff co-rotating twin screw extruder with 8 barrels. The resin mixture was weighed at a rate of 17.5 lb / hour using a gravimetric feeder. Further, using a gravimetric feeder, glass fibers were fed at the barrel section 6 at a rate of 7.5 lb / hr at a total blending rate of 25 lb / hr. The temperature setting of the barrel portion during blending was 330 ° C. in barrel zone 2, barrel zones 3-8, and 340 ° C. for adapters and dies. The temperature of the melt was monitored during the compounding operation using a handheld temperature probe and determined to be in the range of 380-390 ° C. The barrel section 7 was evacuated to achieve a vacuum level of 25 with Hg to remove moisture and other volatile residues from the compound. The blend extrudate was twisted from a die, cooled in a water bath, and then cut into cylindrical pellets of about 3.0 mm length and about 2.7 mm diameter. The composition of Comparative Example C15 was prepared in a similar manner as described above for Example E16.

Injection Molding The pellets obtained from the above compounding process were first dried in an injection molding preparation for about 16 hours (overnight) in a dry convection air oven at 150 ° C. Injection molding was performed for two purposes. 1) Prepare 3.2 mm (0.125 inch) thick ASTM tensile and flexion specimens for mechanical property testing. Type I tensile ASTM specimens and 5 "x 0.5" x 0.125 "bend specimens are injection molded using 30% glass fiber reinforced PEEK injection molding guidelines provided by the supplier (Solvay Specialty Polymers). did. 2) Also, the injection molding of the lap shear overmold test piece was performed with an NMT-treated aluminum grade A-6061 coupon having a length of 4.5 mm × width of 1.75 mm × thickness of 2 mm. These coupons are available from Taiseiplus Corp. Prepared and supplied by Small rectangular polymer specimens were obtained from Taiseiplace Corp. Overmolded aluminum coupons using a three plate mold manufactured and supplied by The plastic rectangular strip overmolded against the aluminum coupon had nominal dimensions, length 4.5 cm, width 1 cm, thickness 3 mm. The pieces of plastic, overmolded with respect to the aluminum coupon, there is overlap area between the two pieces defined by the nominal dimensions of 10 mm × 5 mm, the overlap region of the nominal was set to be 50 mm ^2. The molding temperature used to injection mold the overmolded lap shear assembly was as follows: the barrel temperature settings for the 150 ton Toshiba injection molding machine were the rear / middle / front / nozzle zones, respectively. It was 360/365/371/371 degreeC. The mold temperature was set at 200 ° C and the actual mold temperature performed was about 195 ° C.

Lap Shear Adhesion Test The overmolded aluminum / plastic assembly obtained from the above molding was tested for lap shear strength in an Instron® tensile test apparatus following the guidelines of ASTM D1002. Using positioning fixtures supplied by Taiseplus, hold the assembly in place on the Instron grip and maintain the alignment of the metal and plastic pieces when pulling in the two materials, and the wrap boundary It was confirmed that the force applied to the surface was purely a shear force. A pull rate of 0.05 inches / minute is used for this test, and the lap shear strength of each specimen is divided by the load required to break each assembly divided by the nominal overlap area of the joint. Was calculated by Lap shear strength is referred to interchangeably herein as the adhesive strength of the plastic to the metal substrate.

Results and Discussion As can be seen from the data listed in Table 3, lap shear adhesion of the composition of Example E16 comprising 52 wt.% PEEK and 17.5 wt.% PEKK [Blend (B-1a) in description]]. The strength is a large difference and performs better than the control composition containing only PEKK (Comparative Example C15). In fact, the adhesion of the composition prepared according to the present invention is about twice that of the control composition. In addition to achieving this greatly improved adhesion to the treated aluminum, the mechanical properties of the composition according to the invention are largely comparable to those of the control composition.

Examples C17-E24: Preparation of Glass Fiber Reinforced Composition In Examples E19-E24 of Table 4, the two polymer components of the composition (PAEK-1 and PAEK-2) were initially mixed in a 5 gallon drum for 20 minutes. Tumble blended to produce a resin premix. The premix was then weighed into the feed port of a 25 mm Berstorff co-rotating twin screw extruder with 8 barrels. The resin mixture was weighed at a rate of 12.6 lb / hour using a gravimetric feeder. Further, using a gravimetric feeder, glass fibers were fed at the barrel section 6 at a rate of 5.4 lb / hr at a total blending rate of 18 lb / hr. The temperature setting of the barrel portion during blending was 330 ° C. in barrel zone 2, barrel zones 3-8, and 340 ° C. for adapters and dies. The temperature of the melt was monitored during the compounding operation using a handheld temperature probe and determined to be in the range of 380-390 ° C. The barrel section 7 was evacuated to achieve a vacuum level of 25 with Hg to remove moisture and other volatile residues from the compound. The blend extrudate was twisted from a die, cooled in a water bath, and then cut into cylindrical pellets of about 3.0 mm length and about 2.7 mm diameter. A composition for Control C15 was prepared in a similar manner as described above for Examples E19-E24. The control compositions C17 and C18 were the same as C15 except that the barrel settings at the time of blending were 300 ° C. for barrel zone 2, 3 to 8 for barrel zones, and 340 ° C. for adapters and dies. It was prepared as follows.

The melting temperature T _m was determined as the peak temperature of the melting endotherm in the second thermal scan at DSC at 20 ° C./min.

Examples C25-E33: Adhesion of Compositions C15, C17, and C18, and E19-E14 to Aluminum These examples were applied to an aluminum A-6061 substrate using a poly (aryl ether) adhesive composition. Demonstrate the adhesion of the PEEK / PAEK2 overmold composition. To demonstrate adhesion, a lap shear sample was formed and lap shear stress was measured according to the ASTM D1002 standard with a grip distance of 3.5 inches at room temperature. Lap shear samples were formed by overmolding a metal substrate with the described PEEK / PAEK-2 composition. The metal substrate was formed from an aluminum 6061 alloy and had a double butt lap joint with a surface area of about 0.25 square inches (“In”).

  The aluminum substrate was laser etched (from Minilase ™, from Tykma Technologies) to form a cross-hatch pattern with a distance of about 100 μm between parallel lines. After etching, the metal substrate was rinsed in acetone or isopropanol and dried in a vacuum oven at about 50 to 100 torr at about 50 to 100 torr.

  The PEEK / PAEK-2 composition was deposited on a metal substrate using injection molding (pellets pre-dried at 120 ° C./25 ″ Hg vacuum for 4 hours). In particular, the metal substrate was preheated to a temperature of about 190 ° C. to about 200 ° C. in an oven and then in a hot plate. The preheated substrate was then placed in an injection mold heated to about 199 ° C. The PEEK / PAEK-2 composition was then injected into the mold at a temperature of about 370 ° C. to about 380 ° C. to form a lap shear sample. The lap shear sample was removed from the mold and continued to cool to room temperature.

  The lap shear stress values measured at 0.05 inches / min listed in Table 5 are averaged over the number of lap shear samples in the corresponding sample set. Also, Table 5 shows the melting enthalpy indicating the crystallinity of the composition derived from the melting endotherm in the second thermal scan at DSC at 20 ° C./min. Values are expressed relative to the polymer content of the composition, i.e. excluding the filler content. This is obtained by dividing the value measured in the filled composition by the polymer content (= 0.70).

  The results of the lap shear test measurements were similarly reported on the rupture lap shear stress and further analyzed to determine the type of rupture failure. In particular, after failure of the lap shear sample, the sample was analyzed to determine whether the failure was “adhesion”, “aggregation”, “partial aggregation”, or “specimen break”. Adhesion failure was assessed by the absence of visually detectable polymer on the metal and the absence of visually detectable metal on the fracture surface of the sample on the polymer. Cohesive failure was assessed with a visually detectable amount of polymer on the metal, or a visually detectable amount of metal on the fracture surface of the sample on the polymer. Partial cohesive failure was similar to cohesive failure, but showed a decrease in the amount of polymer on metal or metal on polymer. “Specimen rupture” was evaluated by crushing in the bulk polymer, not the metal / polymer interface.

  Referring to Table 5, for the lap shear samples tested, the composition according to the present invention compared to PEEK (C15) while maintaining a good level of crystallinity (> 42.8 J / g heat of fusion). The results demonstrate a significant improvement in adhesion to aluminum. As in E21 and E23, the improvement observed with only 25% by weight of PAEK-2 [ratio of PAEK-2 to (PAEK-1 + PAEK-2)] was observed with PAEK-2 alone and glass fiber [100% by weight PAEK. Surprising based on the C17 and C18 lap shear results, including -2 to (PAEK-1 + PAEK-2) ratio]. These results thus demonstrate that there is a unique combination of adhesion and crystallinity (chemical resistance) in the composition according to the invention.

Examples C34-E36—Adhesion of Composition to Copper Also, the adhesion of three of these compositions to copper was evaluated. The test conditions were the same as in Examples C25 to E33, except that the metal substrate was formed from copper (electrical grade).

  The copper substrate is rinsed with acetone, then air dried and chemically etched by immersion in an aqueous solution containing 12.2% by weight ferric sulfate pentahydrate and 7.8% sulfuric acid (at 65 ° C. 1 minute), rinsed with demineralized water, immersed in an aqueous solution containing 5.5% by weight potassium dichromate and 9.9% by weight sulfuric acid (5 minutes at room temperature) and rinsed with demineralized water. After etching, the metal substrate was rinsed with demineralized water and dried in a vacuum oven at about 120 ° C. at about 50 to about 100 torr.

  Referring to Table 6, for the lap shear samples tested, the composition according to the present invention has a good level of crystallinity (> 42.8 J / g) compared to the comparative composition containing only PEEK (C34). The results demonstrate that the adhesion to copper is significantly improved while maintaining the heat of fusion.

Examples E37-E38: Preparation of Glass Fiber Reinforced Composition In preparing the compositions of Examples E37, E38, and C39 in Table 7, the components of the composition were first tumble blended on a 5 gallon drum for 20 minutes. A premix of resin was prepared. 40% glass-filled PEEK was made from Ketasire® 880KT PEEK as the precursor of the final composition. The precursor compound was made using a Coperion® ZSK26 co-rotating intermeshing extruder. Before the melt exits the extruder and is cooled and pelletized, the upstream barrel temperature is set at 360 ° C, the transition barrel is 350 ° C, the downstream barrel is 340 ° C, and the adapter and die are set at 350 ° C. Met. OCV 910A glass fiber was introduced into the polymer melt downstream of the extruder. The measured melting temperature of the extrudate exiting the die was 390 ° C. obtained with a hand-held temperature probe. The 40% glass-filled PEEK pellets thus obtained and further PEEK (KetaSpire® KT-880P) (for the preparation of C39) or polymer powder PAEK-2 prepared according to Synthesis Examples 6 and 7 (of E37 and E38) The final composition was produced by mixing (for preparation) to obtain a final level of 30% by weight glass fiber in the composition. The premix was then weighed and weighed into the feed port of an 18 mm Leistritz co-rotating twin screw extruder having 8 barrels. The resin mixture was weighed using a weight feeder at a rate of 5-6 lb / hr. In the preparation of C39, the barrel temperature at the time of blending was 370 ° C. in barrel zone 1, barrel zones 2-5, and 355 ° C. for adapters and dies. The temperature of the melt was monitored during the compounding operation using a handheld temperature probe and determined to be in the range of 380-390 ° C. The barrel portion 7 was evacuated to achieve a vacuum level of 8 mmHg to remove moisture and other volatile residues from the compound. The extrudate of the blend was twisted from the die, cooled in a water bath, and then cut into cylindrical pellets having a length of about 3.0 mm and a diameter of 2.7 mm. Compositions E37 and E38 are the same as C39, except that the barrel temperature setting at the time of blending was 280 ° C. in barrel zone 1, barrel zones 2-5, and 345 ° C. for adapters and dies. Prepared by the method

The melting temperature T _m was determined as the peak temperature of the melting endotherm in the second thermal scan at DSC at 20 ° C./min.

C40 and E41-E42: Adhesiveness of Compositions C39, E37, and E38 to Aluminum The adhesiveness of compositions E37, E38, and C39 to aluminum was evaluated in the same manner as in Examples C25 to E33. The results of these tests are reported in Table 8 below.

  Table 8 shows the melting enthalpy (heat) indicating the crystallinity of the composition derived from the melting endotherm in the second thermal scan at DSC at 20 ° C./min.

  Also, in these tests, after failure of the lap shear sample, the sample is analyzed to determine whether the failure is “adhesion”, “aggregation”, “partial aggregation”, or “specimen break”, The meaning of these expressions is the same as described above.

  Referring to Table 8, in the lap shear samples tested, the composition according to the invention maintains a good level of crystallinity (> 30 J / g heat of fusion) compared to PEEK (C45) while The results demonstrate a significant improvement in adhesion to aluminum.

Examples C43-E45: Preparation of Glass Fiber Reinforced Compositions Comparative Example C43 and Example E44 having a ratio of 60/40 PEEK (KetaSpire® KT-880) / PAEK-2 specified in Table 9 below. And a composition of E45 was prepared by tumble blending, in the form of a powder, a polymer that was blended in the desired ratio for about 20 minutes initially to make a polymer premix. This was followed by melt compounding using a 26 mm Coperion® co-rotating intermeshing twin screw extruder having a 48: 1 length to diameter (L / D) ratio. The extruder had 12 barrel portions, barrel portions 2-7 were heated at a temperature setting of 350 ° C, and barrel portions 8-12 and the die were heated to a temperature set point of 360 ° C. The melt temperature recorded for the extrudate upon exiting the die ranged from 394 to 398 ° C. for all compositions. The feed of the extruder is that the polymer components are weighed by an extruder feed hopper, and the glass fiber is used at a ratio corresponding to a level of 30% by weight in each composition of the barrel part 7 using a gravimetric feeder. And weighed. The extruder is 40 lb / hr (18.15 kg / hr), corresponding to a resin feed rate of 28 lb / hr (12.70 kg / hr) and a glass fiber feed rate of 12 lb / hr (5.44 kg / hr). Operating at total processing speed. The extruder screw speed was set to a total of 200 rpm and the extruder torque reading was maintained in the range of 60-70% when all compositions were blended. An evacuation with a vacuum level> 25 at Hg was applied at the barrel 10 during compounding to remove moisture and any possible residual volatiles from the compound. The extrudates from each experiment were twisted, cooled in water and then pelletized to form pellets with a diameter of about 2.7 mm and a length of 3.0 mm.

Example C46～E48: the adhesive strength of the composition C43~E45 to aluminum in these examples demonstrate the adhesion of the blend of the PEEK = PAEK1 different crystallinity and _{T m} and PAEK2 = PEKK. To demonstrate adhesion, lap shear samples were formed and lap shear stress was measured according to the ASTM D1002 standard with a grip distance of 3.5 inches at room temperature. Lap shear samples were formed by overmolding a metal substrate with the described PAEK1 / PAEK2 composition. The metal substrate was formed from an aluminum 6061 alloy and had an X-shaped lap joint with a surface area of about 0.25 square inches (“In”).

  The aluminum substrate was laser etched (from Minilase ™, from Tykma Technologies) to form a cross-hatch pattern with a distance of about 100 μm between parallel lines. After etching, the metal substrate was rinsed in acetone or isopropanol and dried in a vacuum oven at about 50 to 100 torr at about 50 to 100 torr.

  The PAEK1 / PAEK2 composition was deposited on a metal substrate using injection molding (pre-drying the pellets at 120 ° C./25 ″ Hg vacuum for 4 hours). In particular, the metal substrate was preheated to a temperature of about 190 ° C. to about 200 ° C. in an oven followed by a hot plate. The preheated substrate was then placed in an injection mold heated to about 199 ° C. The PAEK-1 / PAEK-2 composition was then injected into the mold at a temperature of about 370 ° C. to about 380 ° C. to form a lap shear sample. The lap shear sample was removed from the mold and continued to cool to room temperature.

  The lap shear stress values measured at 0.05 inches / min listed in Table 10 are averaged over the number of lap shear samples in the corresponding sample set. Table 10 shows the heat of fusion indicating the crystallinity of the composition derived from the endothermic melting in the second thermal scan at DSC at 20 ° C / min.

  The results of the lap shear test measurements were similarly reported on the rupture lap shear stress and further analyzed to determine the type of rupture failure. In particular, after failure of the lap shear sample, the sample was analyzed to determine whether the failure was “adhesion”, “aggregation”, “partial aggregation”, or “specimen break”. Adhesion failure was assessed by the lack of visually detectable polymer on the metal and the lack of visually detectable metal on the fracture surface of the sample on the polymer. Cohesive failure was evaluated with a visually detectable amount of polymer on the metal or a visually detectable amount of metal on the fracture surface of the sample on the polymer. Partial cohesive failure was similar to cohesive failure, but showed a decrease in the amount of polymer on metal or metal on polymer. “Specimen rupture” was evaluated by crushing in the bulk polymer, not the metal / polymer interface.

Referring to Table 10, for the tested lap shear samples, the composition of PAEK2 = PEKK with T _m <315 ° C. (ie, amorphous PEKK) is PAEK 2 = PEKK with T _m > 315 ° C. (ie, crystal The results demonstrate that it exhibits better adhesion while maintaining a better level of crystallinity (> 30 J / g heat of fusion) than a composition of high quality PEKK).

Claims (19)

A method of coating a metal surface, the method comprising:
Applying a polymer composition comprising a polymer blend [blend (B)] comprising a first polyaryletherketone (PAEK-1) and a second polyaryletherketone (PAEK-2) to a metal surface Including
Wherein (PAEK-1) is crystalline, it shows a melting temperature _{T m} of a higher 330 ° C., wherein a (PAEK-2) amorphous or crystalline, shows a melting temperature _{T m} of a 315 ° C. or less, The (PAEK-1) constitutes a blend (B) exceeding 50% by weight,
The method wherein the composition is heated to a temperature above the melting temperature of (PAEK-1) before being applied to the metal surface. The (PAEK-1) includes a repeating unit (R1), and at least 50 mol% of the repeating unit is represented by the following formulas (JA) to (JQ):
Wherein -R 'is equal to or different from each other, halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali Or selected from the group consisting of alkaline earth metal phosphonates, alkyl phosphonates, amines and quaternary ammonium,
-J 'is zero or an integer from 1 to 4, and
-Y 'is an alkylidene group)
The method of claim 1, according to at least one of the following:   The method according to claim 2, wherein at least 50 mol% of the repeating units (R1) are units of the formula (JA), (JB), (JC) or (JO).   The method according to claim 2 or 3, wherein the phenylene moiety in the repeating unit (R1) has a 1,4-bond.   5. A method according to any one of claims 2 to 4, wherein j 'is zero for each occurrence. The following formula (J′-A):
6. A process according to claim 5, comprising at least 98 mol% of repeating units according to   Said (PAEK-2) comprises at least 50 mol% of repeating units (R2) according to at least one of the formulas (JA) to (JQ) according to claim 2, wherein the units (JA) , (JB), and (JQ), the phenylene moiety independently has 1,3- and 1,4-bonds, while the units (JC) to (JP) 5) The method according to any one of claims 1 to 4, wherein the phenylene moiety has a 1,4-bond.   The method of claim 7, wherein j ′ is zero for each occurrence. Blend (B)
At least 98 mol% of formula (J′-A):
(PAEK-1) which is a polyetheretherketone containing repeating units of
-At least 50 mol% of the repeating units are a combination of units of formula (J'-B) and (J "-B), a combination of units of formula (J'-A) and (J'-D), a formula A unit of (J ′ ″-A), a unit of formula (J′-P), or a combination of units of formula (J′-A) and (J ″ -A), wherein the unit is The following formula:
(PAEK-2) according to claim 1, which is a blend (B-1). Blend (B-1)
1) —all repeating units are units of formula (J′-A) (PAEK-1)
A blend (B-1a), wherein all repeating units are a combination of units of formula (J′-B) and (J ″ -B) (PAEK-2),
2) —all repeating units are units of formula (J′-A) (PAEK-1)
A blend (B-1b) comprising (PAEK-2), wherein all repeating units are a combination of units (J′-A) and (J′-D),
3) —all repeating units are units of formula (J′-A) (PAEK-1)
A blend (B-1c) comprising (PAEK-2), wherein all repeating units are repeating units of formula (J′-P),
4) —all repeating units are units of formula (J′-A) (PAEK-1)
A blend (B-1d) comprising: (PAEK-2) wherein at least 50 mol% of the repeating units are repeating units (J ′ ″-A).
5)-PEEK in which at least 98 mol% of the repeating units are units of the formula (J'-A) (PAEK-1);
-Selected from a blend (B-1e) comprising (PAEK-2) which is PAEK in which at least 95 mol% of the repeating units are repeating units (J'-A) and (J ''-A). The method of claim 9.   11. A method according to any one of the preceding claims, wherein the polymer composition comprises a reinforcing filler. The blend (B) is a blend (B-2) comprising (PAEK-2) which is PAEK, and at least 50 mol% of the repeating units are represented by the following formula (J ″ -A) or (J ″ − Q):
The method of claim 1, according to claim 1. The blend (B-2) has at least 50 mol% of repeating units represented by the following formula (J′-A), units (J′-B) and (J ″ -B), or formula (J '-C):
12. The method of claim 11 comprising (PAEK-1) according to. Blend (B-2)
1)-PEEK whose at least 98 mol% repeat units are units of formula (J'-A) (PAEK-1);
A blend (B-2a) comprising (PAEK-2) at least 95 mol% of the repeating unit is PAEK which is the repeating unit (J ″ -A),
2) —PEEK in which at least 98 mol% of the repeating units are units of formula (J′-A) (PAEK-1);
The process according to claim 13, selected from a blend (B-2b) comprising: (PAEK-2), wherein at least 95 mol% of the repeating units are PAEK which is a repeating unit (J ″ -Q). .   A polymer blend selected from the blend (B-1a), blend (B-1c), blend (B-1d), and blend (B-1e) according to claim 10 [blend (B-1)], or A polymer composition comprising the blend (B-2) according to claim 12.   A polymer composition comprising the polymer blends (B-2a) and (B-2b) according to claim 14. A metal surface coated with a polymer composition comprising a polymer blend [blend (B)] comprising a first polyaryletherketone (PAEK-1) and a second polyaryletherketone (PAEK-2) There,
Wherein (PAEK-1) is crystalline, it shows a melting temperature _{T m} of a higher 330 ° C., wherein a (PAEK-2) amorphous or crystalline, shows a melting temperature _{T m} of a 315 ° C. or less, Said (PAEK-1) is a metal surface coated with a polymer composition comprising more than 50% by weight of blend (B).   The metal surface according to claim 17, which is a surface of a wire or a surface of a structural component of an electronic device.   A wire or electronic device comprising at least one surface according to claim 17 or 18, or a component thereof.