CN120153032A

CN120153032A - Polymer compositions suitable for electrostatic discharge applications

Info

Publication number: CN120153032A
Application number: CN202280101130.7A
Authority: CN
Inventors: 钱圣盈; X·L·徐
Original assignee: Solvay Specialty Polymers USA LLC
Current assignee: Solvay Specialty Polymers USA LLC
Priority date: 2022-10-17
Filing date: 2022-10-17
Publication date: 2025-06-13
Also published as: TW202419571A; KR20250088726A; WO2024082079A1; EP4605475A1

Abstract

Disclosed is a polyarylether composition (C) comprising at least one poly (aryl ether ketone) polymer ("PAEK polymer"), at least one electrically conductive carbon nanofiller ("component A1") and at least one non-fibrous filler ("component A2"). An article, particularly for static dissipative applications such as a substrate carrier, comprising a polyarylether composition (C) is disclosed. The polymer composition is suitable for use in electrostatic discharge applications.

Description

Polymer compositions suitable for electrostatic discharge applications

Technical Field

The present invention relates to a reinforced polyarylether composition which is notably suitable for use in electrostatic discharge applications, and to an article comprising or made from the same.

Background

Conductive thermoplastic polymer compositions are known to be useful for preventing electrostatic discharge (ESD). These specialty polymer compositions are typically tailored to span the surface resistivity spectrum and can often be formulated for injection molding or extrusion processes.

A variety of techniques are available to impart conductive properties to the otherwise insulative thermoplastic resin to provide the precise degree of conductivity required for ESD protection. Wherein the conductive filler may be added to the thermoplastic polymer.

Small-sized carbon materials (e.g., nanotubes) are one of the most important filler materials. It may advantageously increase the strength of the polymeric material and make the polymeric material electrically conductive. However, the fiber shapes in combination with their small size make them difficult to uniformly disperse in the polymer.

US2010/0311869 A1 teaches that better dispersion can be obtained when using non-commercially available hollow carbon nanospheres. In order to obtain a desired shape, a complicated process is required to prepare the carbon nanospheres.

US 8,128,844 B2 discloses the use of organic nanoclays in electrically conductive thermoplastic resin compositions to minimize or prevent the tendency of carbon nanotubes to aggregate or to be unexpectedly oriented and can be made to uniformly disperse in the resin. The organonanoclays are typically prepared by organically modifying nanoscale layered silicates.

Among other thermoplastic polymers, poly (aryl ether ketone) (PAEK), particularly Polyetheretherketone (PEEK) and Polyetherketoneketone (PEKK), provide excellent thermal stability, very high stiffness and strength, and truly excellent chemical resistance, including excellent environmental stress cracking resistance. However, they have drawbacks such as poor toughness and impact resistance (with brittle failure) and have a fairly low heat distortion temperature, which makes them generally unsuitable for ESD applications. Accordingly, many efforts have been made to improve the properties of conductive PAEK polymers. For example, WO 2008/003659A1 discloses a polymer composition (C) comprising at least one poly (aryl ether ketone) (PAEK), at least one poly (biphenyl ether sulfone) and at least one fibrous carbon nanofiller, which provides excellent protection against electrostatic discharge, in particular by providing excellent protection against electrostatic discharge, has substantially the same level of toughness as pure poly (biphenyl ether sulfone) (i.e. does not break when tested in the unnotched izod ASTM D4812), and has much higher chemical resistance than poly (biphenyl ether sulfone). However, there is no teaching on how to uniformly disperse the conductive filler.

Disclosure of Invention

The first object of the present invention therefore relates to a polyarylether composition (C) comprising:

at least one poly (arylene ether ketone) polymer (hereinafter "PAEK polymer"),

At least one conductive carbon nanofiller (hereinafter referred to as "component A1"), and

At least one non-fibrous filler (hereinafter referred to as "component A2").

Another object of the present invention relates to an article comprising or made from the polyarylether composition (C), the article having a volume resistivity of from 1.10 ⁺⁵ Ω. cm to 5.10 ⁺¹² Ω. cm measured according to ASTM D257.

Applicants have found that due to the blending of PAEK polymer with component A1 and component A2, the polyarylether composition (C) of the present invention as detailed herein is effective in improving the uniformity of conductivity and thus optimizing the volume and surface resistivity, making the polymeric material more suitable for ESD applications. In addition, the polyarylether composition (C) of the present invention optimizes the molding shrinkage of the filled ESD polymer material without sacrificing its mechanical properties.

Detailed Description

The polyarylether composition (C) according to the present invention may comprise:

at least 40 to less than 89wt.% of at least one PAEK polymer,

At least 1 and at most 10wt.% of this component A1, and

At least 10wt.% and at most 50wt.% of component A2,

The wt.% is based on the total weight of the polyarylether composition (C).

at least 40wt.% and at most 78wt.% of at least one PAEK polymer,

At least 2 and at most 10wt.% of this component A1, and

At least 20wt.% and at most 50wt.% of component A2,

The wt.% is based on the total weight of the polyarylether composition (C).

at least 55wt.% and at most 79wt.% of at least one PAEK polymer,

At least 1 and at most 5wt.% of this component A1, and

At least 20wt.% and at most 40wt.% of component A2,

The wt.% is based on the total weight of the polyarylether composition (C).

The polyarylether composition (C) according to the present invention may further comprise at least one other polymer than PAEK polymer. The other polymer may comprise a polymer carrier in which component A1 is dispersed prior to mixing with the other components of the polyarylether composition (C). Alternatively or additionally, the other polymer may comprise at least one poly (biphenyl ether sulfone) (hereinafter "component A3") and/or at least one polyether sulfone (hereinafter "component A4"). In this case, the combined weight of the at least one PAEK polymer, component A1, one or more optional other polymers (e.g., polymer carrier, component A3, component A4) and component A2 is equal to or less than 100wt.% of the polyarylether composition (C).

The polyarylether composition (C) according to the present invention may further comprise one or more optional additives, typically not more than 10wt.%, based on the total weight of the polyarylether composition (C). The combined weight of the at least one PAEK polymer, component A1, optionally further polymers, component A2 and one or more optional additives is equal to or less than 100wt.% of the polyarylether composition (C).

Poly (aryl ether ketone) (PAEK) polymers

As mentioned previously, the polyarylether composition (C) comprises at least one PAEK polymer.

For the purposes of the present invention, the term "poly (aryl ether ketone)" or "PAEK" is intended to mean any polymer wherein more than 50wt.%, at least 60wt.%, at least 70wt.%, at least 80wt.%, at least 90wt.%, at least 95wt.%, at least 99wt.% of the recurring units are recurring units (R1) having one or more of the following formulas (I) to (V):

Wherein:

Ar is independently a divalent aromatic radical selected from phenylene, biphenylene or naphthylene,

X is independently O, C (=o) or a direct bond,

N is an integer from 0 to 3,

B, c, d and e are 0 or1,

-A is an integer from 1 to 4, and

Preferably d is 0 when b is 1.

The repeating unit (R1) may notably be selected from:

And

Preferably, the repetition (R1) is selected from:

And

More preferably, the repeating unit (R1) is:

For the purposes of the present invention, polyetheretherketone (PEEK) polymers are intended to mean any polymer in which more than 50wt.% of the recurring units are recurring units (R1) of the formula (VII). Preferably, at least 60wt.%, at least 70wt.%, at least 80wt.%, at least 90wt.%, at least 95wt.%, at least 99wt.% of the recurring units of the PEEK polymer are recurring units (R1) of formula (VII). Still more preferably, substantially all of the recurring units of the PEEK polymer are recurring units (R1) having formula (VII). Most preferably, all of the recurring units of the PEEK polymer are recurring units (R1) having formula (VII).

Preferably, the PAEK polymer (such as PEEK polymer) used in the present invention is not sulfonated.

Excellent results are obtained when the PAEK polymer is a Polyetheretherketone (PEEK) homopolymer, i.e. a polymer in which substantially all, if not all, of the repeating units are of formula (VII). A non-limiting example of a suitable commercially available PEEK homopolymer is that from weiks manufacturing company (Victrex Manufacturing ltd.)PEEK from Solvi specialty Polymer Co (Solvay Specialty Polymers)PEEK and Polymer materials from Jilin province, inc. (Jilin Joinature Polymer Co., ltd.)

The PAEK polymer may have an Intrinsic Viscosity (IV) of at least 0.50dl/g, preferably at least 0.60dl/g, more preferably at least 0.70dl/g as measured at a PAEK concentration of 0.1g/100ml with 95% -98% sulfuric acid (d=1.84 g/ml).

PAEK polymers, such as PEEK polymers, may have a melt viscosity of up to 0.25kPa-s, but preferably less than 0.20kPa-s and most preferably less than 0.18kPa-s at a shear rate of 400 ℃ and 1000s ^-1 as measured using a capillary rheometer according to ASTM D3835. PAEK polymers, such as PEEK polymers, may have melt viscosities as low as 0.05 kPa-s.

PAEK polymers, such as PEEK polymers, may have melt viscosities ranging from 0.05kPa-s to 0.25kPa-s, preferably from 0.06kPa-s to 0.20kPa-s, preferably from 0.07kPa-s to 0.18kPa-s, preferably from 0.08kPa-s to 0.15kPa-s, at a shear rate of 400 ℃ and 1000s ^-1 as measured using a capillary rheometer according to ASTM D3835.

For capillary rheometers, kayeness Galaxy V rheometers (model 8052 DM) can be used.

PAEK polymers, such as PEEK polymers, may be prepared by any method.

One method well known in the art includes reacting a substantially equimolar mixture of at least one bisphenol and at least one dihalobenzene-type compound or at least one halophenol compound, as described in Canadian patent No. 847,963. Non-limiting examples of bisphenols which may be used in the process are hydroquinone, 4' -dihydroxybiphenyl and 4,4' -dihydroxybenzophenone, non-limiting examples of dihalobenzene compounds which may be used in the process are 4,4' -difluorobenzophenone, 4' -dichlorobenzophenone and 4-chloro-4 ' -fluorobenzophenone, and non-limiting examples of halophenols which may be used in the process are 4- (4-chlorobenzoyl) phenol and (4-fluorobenzoyl) phenol. Accordingly, PEEK homopolymer may notably be produced by a nucleophilic process as described, for example, in U.S. patent No. 4,176,222, the entire contents of which are incorporated herein by reference.

Another method of producing PEEK homopolymer well known in the art includes electrophilic polymerization of phenoxy benzoic acid using alkanesulfonic acid as a solvent and in the presence of a condensing agent, such as the method described in us patent 6,566,484, the entire contents of which are incorporated herein by reference. Other poly (aryl ether ketones) can be produced by the same process starting from monomers other than phenoxy benzoic acid, such as those described in U.S. patent application 2003/0130476, the entire contents of which are also incorporated herein by reference.

The polyarylether composition (C) may comprise one and only one PAEK polymer. Alternatively, it may comprise two, three, or even more than three PAEK polymers. Certain preferred mixtures of PAEK polymers are mixtures consisting of (i) at least one poly (aryl ether ketone) (PAEK) -a) wherein greater than 50wt.% of the recurring units, preferably substantially all of the recurring units, and still more preferably all of the recurring units have the formula:

(ii) Wherein greater than 50wt.% of the repeating units, preferably substantially all of the repeating units, and still more preferably all of the repeating units have at least one poly (aryl ether ketone) (PAEK) -b of the formula:

And optionally further, (iii) at least one other poly (aryl ether ketone) (PAEK) -c different from poly (aryl ether ketone) (PAEK) -a and (PAEK) -b), in particular, a mixture consisting of (i) at least one poly (aryl ether ketone) (PAEK) -a wherein substantially all, if not all, of the repeating units have the formula (VII), (ii) at least one poly (aryl ether ketone) (PAEK) -b wherein substantially all, if not all, of the repeating units have the formula (IX), and still more particularly, binary mixtures of (i) one poly (aryl ether ketone) (PAEK) -a wherein all of the repeating units have the formula (VII), and (ii) one poly (aryl ether ketone) (PAEK) -b wherein all of the repeating units have the formula (IX).

The amount of PAEK polymer is at least 40wt.%, preferably at least 41wt.%, or at least 42wt.%, or at least 43wt.%, or at least 44wt.%, or at least 45wt.%, or at least 47wt.%, or at least 49wt.%, or at least 55wt.% and/or less than 89wt.%, preferably at most 88wt.%, or at most 87wt.%, at most 86wt.%, or at most 85wt.%, or at most 80wt.%, or at most 79wt.%, or at most 78wt.%, or at most 75wt.%, based on the total weight of the polyarylether composition (C).

Conductive carbon nanofiller (component A1)

Component A1 is at least one conductive carbon nanofiller comprising elemental carbon. Typically, greater than 90wt.% of the nanofiller consists of elemental carbon. Preferably, greater than 95wt.% of the nanofiller consists of elemental carbon. Still more preferably, greater than 99wt.% of the nanofiller consists of elemental carbon. Good results are obtained when the nanofiller consists essentially of elemental carbon.

At least one conductive carbon nanofiller useful in the present invention may be metallized. However, the at least one conductive carbon nanofiller is preferably not metallized.

From a practical point of view, any nanofiller is three-dimensional and thus can be notably characterized by three characteristic dimensions ("length", "width" and "height"). However, some nanofillers are such that two of their characteristic dimensions are each significantly lower than the third characteristic dimension. The term "significantly lower" is generally understood to mean "more than 10 times lower" and preferably "more than 100 times lower". Specifically, for the purposes of the present invention, a carbon nanofiller has a fibrous shape, meaning that two of its characteristic dimensions ("width" and "height") are on average (by number) significantly smaller than the third dimension ("length"), and because the width of the fibrous nanofiller is typically close to the height and the base of the fibrous nanofiller is typically circular in shape, the width and height are typically understood by the skilled artisan as unique parameters, namely the diameter of the fibrous nanofiller. The fibrous nanofiller will thus generally be characterized by a number average diameter and a number average length. Generally, such materials have an aspect ratio defined as the ratio between the number average length to the number average diameter of at least 5, at least 10, at least 20, or at least 50, or at least 100.

Component A1 is at least one fibrous carbon nanofiller, which generally has a number average diameter of less than 1000nm, preferably less than 500nm, and more preferably at most 200nm.

The at least one fibrous carbon nanofiller may have a number average diameter (when in bundles or strips) from 1 nanometer (nm) to 3.5nm or 4 nm. The at least one fibrous carbon nanofiller may have a number average length of at least 1 μm. The at least one fibrous carbon nanofiller may have an average aspect ratio defined as the number average length divided by the number average diameter of 100 or more. The fibrous carbon nanofiller may have an average aspect ratio of 1000 or greater.

The number average diameter and number average length of the fibrous carbon nanofiller may be determined by any technique known to those skilled in the art, and advantageously, direct measurement of micrographs obtained by Scanning Electron Microscopy (SEM) in combination with software image analysis techniques may be used.

At least one fibrous carbon nanofiller contains greater than 65% carbon. Preferably, at least one fibrous carbon nanofiller contains at least 90% carbon, and more preferably at least 95% carbon.

Component A1 preferably has a volume resistivity of less than 2.10 10 ^-2. OMEGA.cm, or at most 1.10 10 ^-2. OMEGA.cm, or at most 5.10 10 ^-3. OMEGA.cm, or at most 3.10 10 ^-3. OMEGA.cm, or at most 2.10 10 ^-3. OMEGA.cm, or at most 1.10 10 ^-3. OMEGA.cm. Component A1 preferably has a volume resistivity of at least 1.10 10 ^-6 Ω.cm, or at least 5.10 10 ^-6 Ω.cm, or at least 1.10 10 ^-5 Ω.cm. Component A1 may have a volume resistivity of from 1.10 ^-4. OMEGA.cm to 20.10 ^-4. OMEGA.cm.

At least one carbon nanofiller (component A1) is selected from the group consisting of carbon nanotubes, surface modified carbon nanotubes, carbon nanostructures, and any combination thereof.

Carbon Nanotubes (CNTs) are intended to mean any material whose structure comprises at least one graphene layer wound in the form of a hollow cylinder, at least one of the ends of which is, and preferably at each end, covered by a half-molecular fullerene. The term "cylinder" with broad geometrical meaning must be understood as a surface resulting from a linear rotation parallel to a fixed linear axis, resulting in a curve around said axis. As examples of possible shapes of the curve, circles and ellipses may be cited notably.

When the structures of carbon nanotubes useful in the present invention comprise no more than one graphene monolayer, the carbon nanotubes in this case are commonly referred to as "single-walled carbon nanotubes" (SWCNTs).

While structures useful in the present invention may include a coaxial assembly of two SWCNTs (meaning one SWCNT nested within the other), carbon nanotubes in this case are commonly referred to as "double-walled carbon nanotubes" (DWCNTs).

When the structures of carbon nanotubes useful in the present invention include a coaxial assembly of several SWCNTs (nested SWCNTs), the carbon nanotubes are in this case commonly referred to as "multi-walled carbon nanotubes" (MWCNTs). MWCNTs typically comprise more than 3, preferably more than 6, and more preferably more than 10 co-axial SWCNTs and/or less than 60, preferably less than 40, and more preferably less than 20 co-axial SWCNTs.

In the context of the present disclosure, the term "carbon nanotube" also includes carbon nanoribbons (e.g., ribbons of SWCNTs or MWCNTs) that represent bundles of carbon nanotubes.

Such carbon nanotubes are preferably selected from the group consisting of SWCNT, DWCNT, MWCNT, strips thereof, and any combination thereof, and more preferably from MWCNTs.

The number average diameter of the carbon nanotubes useful in the present invention can vary widely, notably depending on whether SWCNT, DWCNT or MWCNT are used. Thus, the number average diameter of SWCNTs is typically greater than 0.3nm, and preferably greater than 0.6nm, and furthermore, the diameter of SWCNTs is typically less than 3.0nm, and preferably less than 2.0nm. The number average diameter of the DWCNTs is generally at least 0.5nm and preferably greater than 0.8nm, which is generally less than 6nm, preferably less than 5nm, and more preferably less than 4nm. The MWCNTs typically have a number average diameter of at least 3nm and preferably greater than 6nm, and typically less than 60nm, preferably less than 40nm, and more preferably less than 20nm. Some suitable MWCNTs have a number average diameter from about 10 to about 15 nm.

The carbon nanotubes useful in the present invention typically have a length significantly greater than their diameter (see, e.g., kirk-Othmer Encyclopedia of Chemical Technology [ encyclopedia of chemical engineering techniques ] (-John Wiley and Sons 2005), volume 17, nanotechnology [ Nanotechnology ], pages 2 to 4). In particular, the number average length diameters (measured along their longitudinal axes) of the carbon nanotubes that can be used according to the present invention can be hundreds or even thousands of times higher than their number average diameter. This number average length is typically greater than 100nm, preferably greater than 1 micron, and more preferably greater than 3 microns and/or is typically less than 100 microns, preferably less than 50 microns, more preferably less than 30 microns.

The number average diameter and number average length of the carbon nanotubes may be determined by any technique known to those skilled in the art, and advantageously, direct measurement of micrographs obtained by Scanning Electron Microscopy (SEM) in combination with software image analysis techniques may be used.

The carbon nanotubes useful in the present invention may be fabricated by any known technique. Non-limiting examples of such methods include arc discharge, pulsed Laser Vaporization (PLV), chemical Vapor Deposition (CVD), and vapor phase processes. Arcing is a plasma-based process that uses solid carbon electrodes for MWCNTs, or uses carbon composites for SWCNTs. The Pulsed Laser Vaporization (PLV) process is basically used to produce SWCNTs, which use a high power pulsed laser aimed at powdered graphite loaded with a metal catalyst. Chemical Vapor Deposition (CVD) may be used to manufacture both SWCNTs and MWCNTs by flowing a heated precursor gas over a metal catalyst. Furthermore, gas phase processes can be used to produce both SWCNTs and MWCNTs.

Carbon nanotubes typically have an elemental carbon purity of greater than 65%, the remainder possibly consisting of residual catalytic impurities. Preferably, the carbon nanotubes contain at least 90% elemental carbon, and more preferably at least 95% elemental carbon.

Preferably, the carbon nanotubes have a volume resistivity of from 10 ^-2 to 10 ^-6 Ω.cm, preferably from 10 ^-3 to 10 ^-5 Ω.cm.

SWCNT is notably commercially available from Sumitomo Shoji, japan co. DWCNT is commercially available from Nanograf. MWCNTs are notably commercially available from the cabo catalysis company (Hyperion Catalysis), the japanese triple well product company (Mitsui Bussan), nikkisou, nanocyl, the application science company (APPLIED SCIENCES), the Shenzhen norboy science and technology company (Shenzhen Nanotech), CNI, the nanchang solar nanotechnology company (Sun Nanotech) and Iljin Nanotech. Suitable MWCNTs include those having a purity as low as 90% C purityNC7000MWCNT grade or C purity with a C purity of 95%NC3100MWCNT grade, both from Nanocyl (belgium).NC7000MWCNT has an average diameter of 9.5 nm, an average length of 1.5 μm, a BET surface area of 250-300m ²/g and a volume resistivity of 1.10 ^-4 Ω. Other suitable sources of carbon nanotubes are those from the Haibulong catalytic International company (Hyperion Catalysis International)MWCNTs having an outer diameter of about 10 nanometers and a length exceeding 10 microns.

As mentioned previously, component A1 useful in the present invention may be at least one surface modified carbon nanotube, i.e. the outer surface of the carbon nanotube may be chemically modified by functional groups, for example to increase its compatibility with at least one PAEK polymer. The functionalization of the carbon nanotubes can be of non-covalent or covalent nature, notably as explained in Kirk-Othmer [ Kirk-otter ], encyclopedia of chemical technology (Encyclopedia of Chemical Technology), supra, pages 8 to 9. Covalent functionalization is generally preferred and can be achieved in a conventional manner by treating the carbon nanotubes with reagents like oxidants, acids and bases. The functional group may notably be a carboxyl group, an ester group, a ketone group, a sulfonic acid group, a sulfonyl group or an amino group.

In a preferred embodiment, the surface-modified carbon nanotubes are amino-grafted carbon nanotubes, notably as disclosed by Z.Cao et al/Applied Surface Science [ applied surface science ],353 (2015), pages 873-881.

The number average diameter and number average length of the surface-modified carbon nanotubes useful in the present invention can vary widely, notably depending on the SWCNT, DWCNT or MWCNT prior to modification.

As mentioned previously, component A1 useful in the present invention may be a carbon nanostructure. The carbon nanostructures are typically chemically cross-linked carbon nanotubes.

Crosslinked carbon nanotubes are notably commercially available product Athlos ^TM from cabot corporation (Cabot Corporation).

The number average diameter and number average length of carbon nanotubes that can be used in the nanostructures of the present invention, notably chemically cross-linked, can vary widely, notably depending on the SWCNT, DWCNT, or MWCNT they are before cross-linking.

Advantageously, component A1 does not comprise hollow carbon nanospheres.

Component A1 may have a specific surface area (BET) of from 100 to 800m ²/g, preferably from 150 to 600m ²/g, more preferably from 200 to 350m ²/g, and most preferably from 200 to 300m ²/g, as measured by The Brunauer-Emmett-Teller method described in Journal of AMERICAN CHEMICAL Society of America, 60,309 (1938).

The amount of component A1 is at least 1wt.%, preferably at least 1.5wt.%, or more preferably at least 2wt.%, and at most 10wt.%, preferably at most 5wt.%, more preferably at most 4wt.%, based on the total weight of the polyarylether composition (C).

Because component A1 may be difficult to handle due to its nanostructure, component A1 may first be dispersed in a polymer carrier to form a nanofiller masterbatch ("MB"). The PAEK polymer, nanofiller MB, at least one non-fibrous filler (component A2), and any optional components or additives are then fed into a mixer, preferably a melt mixer. The polymer carrier is preferably the same as but may be different from the PAEK polymer of the polyarylether composition (C). Typically the polymeric carrier is selected from polyaryletherketone polymers, such as those comprising greater than 50wt.% of the repeating units (R1) described herein having any of formulas (I) to (XXI), but may also comprise or consist of poly (biphenyl ether sulfone) or polyethersulfone. The polymer carrier is preferably the same as the PAEK polymer used in the polyarylether composition (C), and both the polymer carrier and the PAEK polymer comprise more than 50wt.% of recurring units (R1) having formula (VII).

Non-fibrous fillers (component A2)

The non-fibrous filler (component A2) is herein considered to have a three-dimensional structure having a length, a width and a thickness (or height).

The dimensions (length, width, thickness) of the non-fibrous filler can be determined by direct measurement on a micrograph obtained by a Scanning Electron Microscope (SEM).

The average dimensions (i.e., length, width, and thickness) of the non-fibrous filler may be taken as the average length of component A2 prior to incorporation into the polyarylether composition (C), or may be taken as the average dimensions of component A2 in the polyarylether composition (C).

The non-fibrous filler (component A2) may be a particulate filler. The particulate filler has a low aspect ratio of less than 2, defined as the ratio of its largest dimension to its smallest dimension. The particulate filler is generally spherical or oval in shape. Examples of particulate fillers are zinc oxide, zinc sulfide, silica, dolomite, aluminum oxide, calcium sulfate, calcium carbonate, titanium oxide, clay, glass frit, nickel carbonate, iron oxide, quartz powder, magnesium carbonate, fluorocarbon resin, barium sulfate, graphite, and carbon powder.

The non-fibrous filler (component A2) may be in the form of a sheet or a plate. The platy or platy filler can have an aspect ratio defined as the ratio of its largest dimension to its smallest dimension of greater than 5, preferably at least 10. The sheet-like or plate-like filler has a substantially two-dimensional shape, meaning that one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length), like a thin plate. Examples of platy or platy fillers are talc, kaolin, mica and glass flakes.

The glass flakes as component A2 are silica-based glass compounds containing several metal oxides that can be tailored to produce different types of glass. The primary 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 hinder crystallization. Any glass type may be used in the glass filler, such as A, C, D, E, M, S, R, T glass or mixtures thereof, preferably C or E glass. The C glass contains an alkaline component and has high acid resistance. The E-glass contains almost no alkali, and thus it has high stability in the resin and no conductivity.

The glass flakes as component A2 preferably comprise or consist of glass flakes with C-glass or E-glass. A suitable glass sheet (C) having E or C glass is obtained from Nitro Kabushiki Kaisha (NSG) asAre commercially available. The E-glass flakes are particularly effective in preventing warpage and improving dimensional accuracy of precision parts made of thermoplastic polymers.Glass flakes are also commercially available from NSG and have an average thickness of 0.4 to 1 micron and are suitable for fine and thin molded products. In some embodiments, the glass flakes may be granular. For example with E-glassParticulate glass flakes are commercially available from japan plate and nitrate co (NSG).

Mica in the form of platy fillers, e.g. from imery corporation (imery)) Good results were obtained. For example, phlogopite mica products200-HK is a platy mineral with an average particle size of 60 microns.

The non-fibrous fillers (component A2) useful in the present invention are preferably not electrically conductive.

Preferably, the non-fibrous filler (component A2) has an average particle size distribution (also referred to as d ₅₀) ranging from 1 to 300 μm, preferably from 10 to 200 μm, preferably from 10 to 180 μm, as measured by electron microscopy or laser light scattering in isopropanol.

Component A2 may preferably be selected from the group consisting of mica, metal coated mica, glass flake, wollastonite, talc, and any combination thereof.

The non-fibrous filler (component A2) is preferably not functionalized with at least one of sulfonic acid groups, phosphine groups, carboxylic groups (e.g., carboxylic acid groups), amino groups, hydroxyl groups, or thiol groups.

The non-fibrous filler (component A2) does not include organically modified mica, such as organically modified mica with an organic phosphate or ammonium salt substituted with a C ₁₂-C₃₆ alkyl or C ₅-C₃₀ aromatic group.

When a platy filler is present in the polyarylether composition (C), the average thickness of the flakes may be from 0.1 to 5 μm, preferably from 0.2 to 2 μm, more preferably from 0.5 to 1.5 μm as measured by electron microscopy.

The non-fibrous filler (component A2) is more than 10wt.%, preferably at least 15wt.%, more preferably at least 20wt.%, still more preferably at least 30wt.%, and/or at most 50wt.%, preferably at most 40wt.%, more preferably at most 35wt.%, based on the total weight of the polyarylether composition (C).

Furthermore, no pretreatment is required for combining component A1 with component A2 prior to blending. For example, component A1 need not be coated onto component A2.

Wherein component A1 and component A2 are present in the polyarylether composition (C), the weight of PAEK polymer is at least 30wt.%, or at least 40wt.%, or at least 50wt.% and/or at most 90wt.%, preferably at most 80wt.%, more preferably at most 70wt.%, based on the total weight of the polyarylether composition (C).

Wherein component A1 and component A2 are present in the polyarylether composition (C), the PAEK polymer is preferably not crosslinked with component A1 and/or component A2. In particular, there is no linkage between the PAEK polymer and component A2.

Optionally other polymers

The polyarylether composition (C) may further comprise at least one poly (biphenyl ether sulfone) (hereinafter referred to as "component A3") and/or at least one polyether sulfone (hereinafter referred to as "component A4").

For the purposes of the present invention, poly (biphenyl ether sulfone) is intended to mean a polycondensation polymer wherein at least 50 mole%, at least 60 mole%, at least 70 mole%, at least 80 mole%, at least 90 mole%, at least 95 mole%, or at least 99 mole% of the recurring units are recurring units (R2) selected from the group consisting of:

And

The use of the repeating unit having formula (2) in the repeating unit (R2) generally provides the best overall cost-property balance and highest level of toughness. For the purposes of the present invention, polyphenylsulfone (PPSU) polymers are intended to mean any polycondensation polymer in which at least 50mol% of the recurring units are recurring units (R2) of formula (2).

The poly (biphenyl ether sulfone) (component A3) may notably be a homopolymer, a random, alternating or block copolymer.

When the poly (biphenyl ether sulfone) (component A3) is a copolymer, its repeating units may notably consist of (i) a repeating unit (R2) having at least two different formulae selected from formulae (2) to (6), or (ii) a repeating unit (R2) having one or more formulae (2) to (6) (in particular a repeating unit having formula (2)) and a repeating unit (R2) (different from the repeating unit (R2)), such as:

And

Preferably more than 70mol%, more preferably more than 85mol% of the recurring units of the poly (biphenyl ether sulfone) (component A3) are recurring units (R2) of the formula (2). Still more preferably, substantially all of the recurring units of the poly (biphenyl ether sulfone) (component A3) are recurring units (R2) having formula (2). Most preferably, all the recurring units of the poly (biphenyl ether sulfone) (component A3) are recurring units (R2) having formula (2).

Excellent results are generally obtained when the poly (biphenyl ether sulfone) (component A3) is a polyphenylsulfone homopolymer, i.e., substantially all, if not all, of the repeating units are polymers having formula (2). From Sorve specialty Polymer Co., USA, solvay Specialty Polymers USA, L.L.C.)Polyphenylsulfone is an example of a polyphenylsulfone homopolymer (PPSU).

The poly (biphenyl ether sulfone) (component A3) may be prepared by any method. Methods well known in the art are those described in U.S. Pat. Nos. 3,634,355, 4,008,203, 4,108,837 and 4,175,175, which are incorporated herein by reference in their entirety.

The polyarylether composition (C) may comprise one and only one poly (biphenyl ether sulfone) (component A3). Alternatively, it may comprise two, three, or even more than three poly (biphenyl ether sulfones) (component A3).

For the purposes of the present invention, polyethersulfone (component A4) represents any polymer comprising at least 50 mole percent, at least 60 mole percent, at least 70 mole percent, at least 80 mole percent, at least 90 mole percent, at least 95 mole percent, or at least 99 mole percent of repeat units (R _PES) having the formula (J):

mol.% is based on the total moles of repeating units in the polyethersulfone polymer.

Polyethersulfone polymers may be prepared by known methods, such as the condensation of bisphenol S and dichlorodiphenolsulfone, and are notably from Sorve specialty polymers, inc. of AmericaPESU is available.

When poly (biphenyl ether sulfone) (component A3) and/or polyethersulfone (component A4) are present in the polyarylether composition (C), the weight of PAEK polymer is at least 50wt.%, preferably at least 60wt.%, more preferably at least 70wt.% and/or at most 90wt.%, preferably at most 80wt.%, based on the combined weight of PAEK polymer and component A3/component A4 in the polyarylether composition (C).

The polyarylether composition (C) may further comprise a polymer carrier, which is different from the PAEK polymer present in the polyarylether composition (C). Typically the polymeric carrier may be selected from polyaryletherketone polymers, such as those comprising more than 50wt.% of the repeating units (R1) described herein having any of formulas (I) to (XXI), but may also comprise or consist of poly (biphenyl ether sulfone) or polyethersulfone. The polymeric support preferably comprises greater than 50wt.% of a repeating unit (R1) having formula (VII). When such a polymer carrier different from the PAEK polymer is present in the polyarylether composition (C), the weight of the PAEK polymer is at least 50wt.%, preferably at least 60wt.%, more preferably at least 70wt.% and/or at most 95wt.%, preferably at most 90wt.%, based on the combined weight of PAEK polymer and polymer carrier in the polyarylether composition (C).

One or more optional additives

In some embodiments, the polyarylether composition (C) according to the present invention comprises additives selected from the group consisting of ultraviolet ("UV") stabilizers, heat stabilizers, pigments, dyes, flame retardants, impact modifiers, lubricants, nucleating agents, antioxidants, processing aids, and any combination of one or more thereof.

In some embodiments wherein the polyarylether composition (C) comprises optional additives, the total concentration of additives is no more than 15wt.%, no more than 10wt.%, no more than 5wt.%, no more than 1wt.%, no more than 0.5wt.%, no more than 0.4wt.%, no more than 0.3wt.%, no more than 0.2wt.%, or no more than 0.1wt.%.

One or more pigments may be particularly desirable additives in the polyarylether composition (C) to make white, black or colored articles. The pigment may be a black pigment such as carbon black, a white pigment such as zinc oxide, zinc sulfide, lithopone, antimony white and titanium dioxide (rutile or anatase, preferably rutile), and/or a colored pigment. The pigment is generally present in an amount of from 0 to 6wt%, preferably from 0.05 to 5wt% and in particular from 0.1 to 3wt%, based on the total weight of the polyarylether composition (C).

The antioxidant may be a particularly desirable additive in the polyarylether composition (C). The antioxidant can improve the thermal stability and photostability of the polyarylether composition (C). For example, antioxidants that are heat stabilizers can improve the thermal stability of the composition during manufacture (or in high heat application environments), for example, by making the polymer processable at high temperatures while helping to prevent degradation of the polymer.

Process for preparing polyarylether composition (C)

The polyarylether composition (C) according to the present invention may be prepared using methods well known in the art.

For example, the polyarylether composition (C) is prepared by melt blending at least one PAEK polymer, at least one conductive carbon nanofiller (component A1), at least one non-fibrous filler (component A2), and any optional components or additives. Any suitable melt blending method may be used to combine the components of the polyarylether composition (C). For example, all components may be fed into a melt mixer, such as a single or twin screw extruder, a stirrer, a single or twin screw kneader, or a Banbury (Banbury) mixer. These components may be added all at once to the melt mixer or stepwise in portions. When the components are added stepwise in batches, a portion of the components is first added and then melt mixed with the remainder of the subsequently added components until a well mixed composition is obtained.

Because the carbon nanofiller (component A1) may be difficult to handle due to its nanostructure, component A1 may first be dispersed into a polymer carrier to form a nanofiller masterbatch ("MB"). The PAEK polymer, nanofiller MB (containing component A1), at least one non-fibrous filler (component A2), and any optional additives are then fed into a melt mixer. The polymer carrier in MB is preferably the same as but may be different from the PAEK polymer in the polyarylether composition (C). Typically the polymeric carrier is selected from polyaryletherketone polymers, such as those comprising greater than 50wt.% of the repeating units (R1) described herein having any of formulas (I) to (XXI), but may also comprise or consist of poly (biphenyl ether sulfone) or polyethersulfone. The polymer carrier is preferably the same as the PAEK polymer used in the polyarylether composition (C), and both the polymer carrier and the PAEK polymer comprise more than 50wt.% of recurring units (R1) having formula (VII).

Article of manufacture

As mentioned previously, the invention further relates to an article, preferably a shaped article, comprising or made from said polyarylether composition (C).

The polyarylether composition (C) as detailed above may be processed by usual melt processing techniques, notably including extrusion molding, injection molding and compression molding, to provide shaped articles.

Such articles have a volume resistivity of from 1.10 ⁺⁵ Ω. cm to 5.10 ⁺¹² Ω. cm measured according to ASTM D257.

The article has been found to have a surface resistivity of at least 10 ⁶ and at most 10 ⁹ Ω/sq.

The volume resistivity is the resistance to leakage current through the body of insulating material. The surface resistivity is the resistance of leakage current along the surface of the insulating material.

It has also been found that the article has a flow molding shrinkage or transverse molding shrinkage of at most 1.0%, at most 0.9%, at most 0.8%, or at most 0.7%, preferably from 0.1% to 0.6%, more preferably from 0.2% to 0.5% based on method ASTM D955.

As used herein, the term "mold shrinkage" refers to shrinkage of a polymer upon cooling after its molding process. It is typically used to properly process injection molding such that the final part dimensions are as desired. Flow molding shrinkage refers to molding shrinkage in the flow direction. Transverse (or cross-flow) mold shrinkage refers to mold shrinkage in the transverse (cross-flow) direction.

The shaped articles of the invention are preferably selected from the group consisting of (i) extruded profiles, preferably selected from the group consisting of rods, plates, tubes, pipes or profiles, and (ii) injection molded articles.

According to certain embodiments, the shaped article is in the form of a substantially two-dimensional article, such as a part, such as a film, a sheath, and a sheet, in which one dimension (thickness or height) is significantly smaller than the other two characteristic dimensions (width and length).

According to other embodiments, the shaped article is provided as a three-dimensional part, e.g. extending in three dimensions of space in a substantially similar manner, including in the form of a part having a complex geometry, e.g. having concave or convex portions, possibly including undercuts, inserts, etc.

The polyarylether composition (C) may be used to make static dissipative articles such as, but not limited to, substrate carriers. Substrate carriers may include, but are not limited to, wafer carriers, reticle pods (reticle pods), carriers (shipper), chip trays (chip trays), test sockets (test sockets), head trays (head trays) (read and/or write), fluid tubing, chemical containers, and the like.

The molded articles may include, but are not limited to, part or all of a reticle carrier as shown in U.S. patent nos. 6,513,654 and 6,216,873, a tray carrier as shown in U.S. patent nos. 4,557,382 and 5,253,755, a chip tray as shown in U.S. patent No. 6,857,524, a wafer carrier as shown in U.S. patent No. 6,848,578, each of which is incorporated herein by reference in its entirety.

According to certain embodiments, shaped articles made from the polyarylether composition (C) as detailed above are provided as one or more parts of an electrostatic discharge (ESD) protection device, which may for example be designed for connection to a semiconductor wafer intended for chip manufacturing.

Examples

The invention will now be described with reference to the following examples, which are intended to be illustrative only and are not intended to limit the scope of the invention. As used in the examples, "E" represents an example embodiment of the present invention, and "CE" represents a counterexample.

Material

● PEEK from Solvi specialty Polymer CoKT-890P

● Component A1 MWCNT Multi-walled carbon nanotubes from Mitsubishi gas chemical Co., ltd (Mitsubishi GAS CHEMICAL Co.)NC7000 having an average diameter of 9.5 nm, an average length of 1.5 μm, a BET surface area of 250-300m ²/g and a volume resistivity of 1.10 ^-4. Omega. Cm

The o CNT master batch (CNT MB) is 90wt%10Wt% in KT-890PPEEKNC7000

● Component A2:

O mica in platy form from Eimeri Corp 200-HKo glass flakes very thin E-glass flakes MEG160FY-M03 from Nippon Sheet glass Co., ltd, with an average length of 160 microns (flat surface) and a thickness of 0.7 microns.

Test method

● Tensile Property-ISO 527

Tensile modulus, tensile strength and elongation at break were measured on 5 injection molded ISO 1a type tensile samples (total length=170 mm, gauge length=50 mm, test section width=10 mm, and thickness=4 mm).

● Impact Strength-ISO 180

Notched and unnotched Izod impact strength properties (in kJ/m ²) were measured using 10 injection molded ISO 1A type bars (80.+ -. 2mm in length, 10.+ -. 0.2mm in width, 4.+ -. 0.2mm in thickness).

● Mold shrinkage-ISO 294 (ASTM D955)

The molding shrinkage (%) in the flow direction and molding shrinkage (%) in the transverse direction) was measured on 5 injection-molded substrates having dimensions of 60mm width by 60mm length by 2mm thickness.

● Volume and surface resistivity-ASTM D257

Volume and surface resistivity were measured on 5 injection molded substrates having dimensions of 4 "x 1/8" (length x width x thickness) or 60mm x 2mm (length x width x thickness).

Example 1

The resin and filler were fed into a ZSK-26mm co-rotating twin screw extruder using a gravity feeder, which was adjusted for each run to achieve the target blend ratios in table 1. The compounding conditions for all blending and control are shown in table 2. The set point on the extruder is the same for all runs.

The composition prepared by injection molding process according to ASTM D3641 is then processed to provide a shaped article.

TABLE 1

TABLE 2

Example 2

Three components of the preparation sample E2 are listed in Table 1. The composition and shaped article of example 2 were prepared in the same manner as in example 1.

Comparative example 3

Two components (PEEK, A1) of sample CE3 were prepared and are listed in table 1.

The composition and molded article of comparative example 3 were prepared in the same manner as in example 1.

As shown by the results in table 3, the compositions (E1 and E2) according to the present invention are effective in improving the volume and surface resistivity of the article and render the article suitable for ESD applications. In contrast, CE3 samples with MWCNT alone have poor volume and surface resistivity, beyond what is suitable for ESD applications.

Furthermore, the compositions according to the invention (E1 and E2) optimize the molding shrinkage of the article, reducing the molding shrinkage to 0.5% or 0.6%, compared to CE3, which has much higher flow and transverse molding shrinkage (1.5% and 1.6%, respectively).

TABLE 3 Table 3

* X-flow indicates transverse shrinkage.

The disclosures of all patent applications and publications cited herein are hereby incorporated by reference to the extent that they provide exemplary, procedural or other details supplementary to those set forth herein. The disclosure of any patent, patent application, or publication incorporated by reference herein should be given priority if it conflicts with the description of the present application to the extent that the term "does not become clear". Any incorporation by reference of documents is limited such that no subject matter is incorporated that is contrary to the explicit disclosure herein.

While the preferred embodiment of the present invention has been shown and described, modifications thereof can be made by one skilled in the art without departing from the teachings of the invention. The embodiments described herein are exemplary only and are not limiting. Many variations and modifications of the composition, article, and method are possible and are within the scope of the invention. The scope of protection is therefore not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. Each of the claims is incorporated into this specification as an embodiment of the invention. Thus, the claims are a further description and are an addition to the preferred embodiments of the present invention.

Claims

1. A polyarylene ether composition (C), comprising:

at least one poly(aryletherketone) polymer (PAEK polymer),

at least one conductive carbon nanofiller (component A1), and

At least one non-fibrous filler (component A2).

2. The polyarylene ether composition (C) according to claim 1, wherein the PAEK polymer comprises greater than 50 wt.%, at least 60 wt.%, at least 70 wt.%, at least 80 wt.%, at least 90 wt.%, at least 95 wt.%, at least 99 wt.% of a repeating unit (RPAEK) selected from any of the following formulae (I) to (V), based on the total weight of the repeating units in the _PAEK polymer:

in:

-Ar is independently a divalent aromatic group selected from phenylene, biphenylene or naphthylene,

-X is independently O, C(=O) or a direct bond,

-n is an integer from 0 to 3,

- b, c, d and e are 0 or 1,

-a is an integer from 1 to 4, and

- Preferably, when b is 1, d is 0.

3. The polyarylene ether composition (C) according to claim 1 or 2, wherein the at least one conductive carbon nanofiller (component A1) is selected from the group consisting of carbon nanotubes, surface-modified carbon nanotubes, carbon nanostructures and any combination thereof,

The carbon nanotubes or surface-modified carbon nanotubes are selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, strips thereof, and any combination thereof, preferably multi-walled carbon nanotubes, and

The carbon nanostructures are chemically cross-linked carbon nanotubes.

4 . The polyarylether composition (C) according to claim 3 , wherein the surface-modified carbon nanotubes are amino-grafted carbon nanotubes.

5 . The polyarylene ether composition (C) according to claim 1 , wherein the component A1 does not include hollow carbon nanospheres.

6. The polyarylether composition (C) according to any one of claims 1 to 5, wherein the polyarylether composition (C) comprises at least 1 wt.%, preferably at least 1.5 wt.%, or more preferably at least 2 wt.%, and/or at most 10 wt.%, preferably at most 5 wt.%, more preferably at most 4 wt.% of the component A1, based on the total weight of the polyarylether composition (C).

7. The polyarylether composition (C) according to any one of claims 1 to 6, wherein the component A2 is selected from the group consisting of mica, metal-coated mica, glass flakes, wollastonite, talc, and any combination thereof.

8 . The polyarylene ether composition (C) according to claim 1 , wherein the component A2 is in the form of a plate or sheet.

9. The polyarylene ether composition (C) according to any one of claims 1 to 8, wherein the component A2 is non-conductive.

10. The polyarylene ether composition (C) according to any one of claims 1 to 9, wherein the polyarylene ether composition (C) comprises greater than 10 wt.%, preferably at least 15 wt.%, more preferably at least 20 wt.%, yet more preferably at least 30 wt.%, and/or at most 50 wt.%, preferably at most 40 wt.%, more preferably at most 35 wt.% of component A2, based on the total weight of the polyarylene ether composition (C).

11 . The polyarylene ether composition (C) according to claim 1 , wherein the PAEK polymer is not crosslinked with the component A1 and/or the component A2.

12. The polyarylene ether composition (C) according to any one of claims 1 to 11, comprising:

at least 40 wt.% to less than 89 wt.% of the at least one PAEK polymer,

at least 1 wt.% and at most 10 wt.% of component A1, and

greater than 10 wt.% and up to 50 wt.% of component A2,

The wt. % is based on the total weight of the composition (C).

13. A method for preparing the polyarylene ether composition (C) according to any one of claims 1 to 12, comprising melt blending the PAEK polymer, the conductive carbon nanofiller (component A1), the at least one non-fibrous filler (component A2), and any optional components or additives.

14. The process for preparing a polyarylene ether composition (C) according to claim 13, wherein the component A1 is first dispersed in a polymer carrier to form a nanofiller masterbatch ("MB"), and then wherein the PAEK polymer, the nanofiller MB, the at least one non-fibrous filler (component A2) and any optional components or additives are fed into a melt mixer.

15. A shaped article suitable for electrostatic discharge applications, comprising or made from the polyarylether composition (C) according to any one of claims 1 to 12, the article having a volume resistivity of from 1·10 ⁺⁵ Ω.cm to 5·10 ⁺¹² Ω.cm measured according to ASTM D257.

16. The shaped article according to claim 15, having a surface resistivity of at least 10 ⁶ and at most 10 ⁹ Ω/sq, and having a flow molding shrinkage or a transverse molding shrinkage based on method ASTM D955 of at most 1.0%, at most 0.9%, at most 0.8%, or at most 0.7%, preferably from 0.1% to 0.6%.

17. The molded article according to claim 15 or 16, which is a substrate carrier selected from the group consisting of a wafer carrier, a reticle box, a transporter, a chip tray, a test socket, a head tray, a fluid conduit, and a chemical container.