Poly(ester-imide) polymers and uses thereof

Abstract

The present disclosure relates to poly(ester-imides) ("PEI") that exhibit low dielectric constants and dissipation factor tangents, and uses thereof. Such polymers can be used in the manufacture of articles suitable for portable electronic device components, such as, for example, films and structural parts. The present disclosure further relates to solutions comprising PEI, and uses of the solutions for the manufacture of films or portable electronic device articles or parts.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to European Patent Application Publication No. 22305008.9, filed January 6, 2022, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present disclosure relates to poly(ester-imides) ("PEI") that exhibit low dielectric constants and dissipation factor tangents, and uses thereof. Such polymers can be used in the manufacture of articles suitable for portable electronic device components, such as, for example, films and structural parts. The present disclosure further relates to solutions comprising PEI, and the use of said solutions for the manufacture of films or portable electronic device articles or parts. [Background technology]

[0003] Due to their reduced weight and high mechanical performance, polymer compositions are widely used to manufacture portable electronic device components. To meet the growing demand for device hyper-connectivity, electronic components are becoming increasingly complex. This increased device connectivity is driven primarily by the increased data transfer speeds and network capacity enabled by 5G cellular networks. To meet the demands of 5G networks operating at frequencies up to 100 GHz, dielectric insulating materials must exhibit low dielectric constants (Dk) and dissipation factor (Df), typically less than 4.0 and 0.0035, respectively.

[0004] JP 2009 / 286683 (Asahi Kasei Materials Corp) (D1) and JP 01-185324 (Idemitsu Kosan Co) (D2) do not disclose polymers containing repeating units (I).

[0005] Dielectric constant describes the ability of a material to interact with electromagnetic radiation and disrupt electromagnetic signals (e.g., radio signals) traveling through the material. Thus, the lower the dielectric constant of a material at a given frequency, the less electromagnetic signals are disrupted by the material at that frequency. The dissipation factor is the inverse of the ratio of the capacitive reactance to the resistance of a material at a particular frequency. It measures the electromagnetic energy absorbed and lost (power dissipation) when electromagnetic radiation is applied. The lower the dissipation factor (Df), the less electromagnetic radiation the material absorbs and dissipates, typically as heat.

[0006] The current standard material for dielectric insulating substrates in printed circuit boards (PCBs) and flexible printed circuits (FPCs) is polyimide (PI), which is traditionally prepared in solution form as a polymer precursor, cast into film form, and heat treated to form the final PI film substrate. However, PI suffers from high water uptake, at least in part due to the imide moieties present in each repeat unit. As water is uptake occurs, there is a concomitant increase in Df. In less demanding dielectric applications, this increase in Df was acceptable as it did not affect performance in the frequency range utilized in previous generations of cellular networks (e.g., 4G LTE). However, in the more demanding 5G electronics space, this degradation in performance due to water uptake causes enhanced signal attenuation at higher frequencies. It is therefore desirable to produce a replacement for PI with suitable dielectric performance that can be cast from solution using widely available solvents, with improved dielectric performance in both dry and wet conditions.

[0007] Thus, there is a continuing need to develop compositions and materials that are easily processed into films or portable electronic device articles or components, yet also exhibit desirable dielectric performance, i.e., low dielectric constant and dissipation factor, in both high and low humidity environments.

[0008] The polymers of the present invention have been found to be easily processable into portable electronic device articles or components, such as films, while also exhibiting desirable dielectric performance, such as low dielectric constant and / or dissipation factor, in both high and low humidity environments. Summary of the Invention

[0009] The invention is described in the attached set of claims. The invention relates to a polymer according to any one of claims 1 to 34. The invention also relates to a polymer composition according to any one of claims 35 to 39. The invention also relates to a portable electronic device article or part according to any one of claims 40 to 43. The invention further relates to a solution according to any one of claims 42 to 44. The invention further relates to the use of a solution according to any one of claims 47 to 49 for the manufacture of a film, or a portable electronics article or part, or an automotive or aeronautics or drone article or part, or a metal clad laminate. The invention further relates to a metal clad laminate according to any one of claims 50 to 51.

[0010] More precise and detailed specifications on these topics are provided below.

[0011] definition As used herein, the terms "a," "an," or "the" mean "one or more" or "at least one," and can be used interchangeably, unless otherwise specified. As used herein, the term "and / or" used in a phrase of the form "A and / or B" means A only, B only, or A and B together.

[0012] As used herein, the term "comprise" is synonymous with "including," "containing," or "characterized by" and is intended to be inclusive or open-ended and does not exclude additional, unrecited elements or steps. The term "consisting essentially of" includes the specified materials or steps, as well as those that do not essentially affect the basic characteristics or function of the composition, process, method, or article of manufacture being described. The term "consisting of" excludes any elements, steps, or ingredients not specified.

[0013] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains.

[0014] The term "arylene" as used herein means a divalent unsaturated hydrocarbon radical containing one or more six-membered carbon rings in which the unsaturation may be represented by three conjugated double bonds. Arylene radicals include monocyclic arylenes and polycyclic arylenes.

[0015] "Polycyclic arylene" refers to a divalent unsaturated hydrocarbon radical containing two or more six-membered carbocyclic rings, where the unsaturation may be represented by three conjugated double bonds and where adjacent rings may be linked to each other by one or more bonds, divalent bridging groups such as sulfoxide (-SO-), sulfone (-SO2-), ether (-O-), carbonyl (-CO-), thioether (-S-), alkylene, alkenylene, etc., or may be fused to each other. The arylene radical may be substituted on one or more carbons of the ring with hydroxyl, cyano, alkyl, alkoxyl, alkenyl, halo, haloalkyl, monocyclic aryl, amino, -(C=O)-alkyl, -(C=O)O-alkyl, -(C=O)-haloalkyl, or -(C=O)-(monocyclic aryl). Examples of arylene radicals include, but are not limited to, phenyl, styrylbenzenephenyl, (phenylsulfonyl)phenyl, phenoxyphenyl, phenylalkylphenyl, phenylcarbonylphenyl, biphenyl, triphenyl, anthracenyl, naphthyl, phenanthrenyl, etc. As used herein, the terms and expressions "invention," "present invention," "instant invention," and similar terms and expressions are open-ended and are not intended to limit the subject matter of the invention to any single embodiment, but rather encompass all possible embodiments described.

[0016] The proportion of repeating units in a polymer is expressed as mole % based on the total molar amount of repeating units in the polymer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] polymer: In a first aspect, the present disclosure provides a method for producing a pharmaceutical composition comprising: A repeating unit of formula (I) or a combination of a repeating unit of formula (I) with a repeating unit selected from the group consisting of repeating units of formulae (II), (III) and combinations thereof: [ka] at least 30 mol % of; Repeating units of formula (IV): [ka] (Wherein, Ar is [ka] (In the formula, each occurrence of R is a C-C spiro substituted cycloaliphatic group, -NO, -CN, -OH, or a haloalkyl group; m is an integer from 1 to 3, each occurrence of n is an integer from 0 to 4, provided that at least one occurrence of n is an integer from 1 to 4) [ka] (selected from the group consisting of 1 mol % to 35 mol % of Repeating units of formula (V): [-O-Ar1-O-] (V) (Wherein, Ar1 is C6 to C 18 Arylene or -Ar c -L2-Ar d - and In the formula, Ar c and Ar d are each independently C6 to C 18 arylene, and L2 is a divalent group selected from the group consisting of a bond, -O-, -S-, -SO-, SO2-, -(C=O)-, -(C=O)O-, -(C=O)NH-, -(C=S)S-, -CH=CH-, -C(CH3)2-, and -C(CF3)2-. 10 mol% to 35 mol% of Regarding the polymer comprising The mole percentages are based on the total molar amount of repeat units in the polymer.

[0018] The polymers of the present invention can be described as "poly(ester-imide)s" because their backbones are formed from units linked together by imide (present in repeat unit (IV)) and ester groups. Thus, repeat units (I), (II) (if present), (III) (if present), (IV), (V), (VI) (if present), and (VII) (if present) are linked together by ester groups.

[0019] Repeating unit (I) / Combination of repeating unit (I) with other repeating units (II) and (III) The polymer comprises at least 30 mol % of repeat units of formula (I) or a combination of repeat units of formula (I) and repeat units selected from the group consisting of repeat units of formula (II), (III), and combinations thereof. For example, the polymer can comprise at least 30 mol % of a combination of repeat units (I) and (II), or a combination of repeat units (I) and (III), or a combination of repeat units (I), (II), and (III).

[0020] The total proportion of the repeating units of formula (I) or the combination of the repeating units of formula (I) and the repeating units (II) and / or (III) in the polymer is at least 30 mol%, typically 30 mol% to 99 mol%, preferably 30 mol% to 89 mol%, more preferably 50 mol% to 85 mol%, or 60 mol% to 85 mol%, and even more preferably 60 mol% to 70 mol%, said mol% being based on the total molar amount of the repeating units in the polymer.

[0021] This ratio may be preferably 30 mol% to 99 mol%, more preferably 30 mol% to 89 mol%, even more preferably 30 mol% to 80 mol%, even more preferably 50 mol% to 80 mol%, or 55 mol% to 75 mol%, or 60 mol% to 70 mol%. This ratio may advantageously be 58 mol% to 72 mol%.

[0022] This ratio may be preferably 30.0 mol% to 99.0 mol%, more preferably 30.0 mol% to 89.0 mol%, even more preferably 30.0 mol% to 80.0 mol%, even more preferably 50.0 mol% to 80.0 mol%, or 55.0 to 75.0 mol%, or 60.0 mol% to 70.0 mol%. This ratio may advantageously be 58.0 to 72.0 mol%.

[0023] When repeating units (I) are combined with repeating units (II) and / or (III), the proportion of repeating units (I) is preferably at least 5 mol%, preferably at least 10 mol%, preferably at least 20 mol%, preferably at least 40 mol%, preferably at least 50 mol%.

[0024] Repeating unit of formula (IV) The polymer comprises from 1 mol % to 35 mol % of repeat units of formula (IV) relative to the total molar amount of repeat units in the polymer. This proportion may preferably be from 5 to 35 mol %, or from 10 to 25 mol %. This proportion may advantageously be from 15 to 22 mol %.

[0025] This proportion may be preferably 5.0 to 35.0 mol %, or 10.0 to 25.0 mol %. This proportion may advantageously be 15.0 to 22.0 mol %.

[0026] The repeat unit is of formula (IV): [ka] (Wherein, Ar is [ka] (In the formula, Each occurrence of R in formula (A) is a C-C spiro substituted cycloaliphatic group, -NO, -CN, -OH, or a haloalkyl group; m is an integer from 1 to 3, each occurrence of n is an integer from 0 to 4, provided that at least one occurrence of n is an integer from 1 to 4) [ka] (selected from the group consisting of:

[0027] More specifically, Ar can be represented by the following formula (A): [ka] (In the formula, Each occurrence of R in formula (A) is a C-C spiro substituted cycloaliphatic group, -NO, -CN, -OH, or a haloalkyl group; m is an integer from 1 to 3, each occurrence of n is an integer from 0 to 4, provided that at least one occurrence of n is an integer from 1 to 4).

[0028] m can be 1, 2, or 3.

[0029] This "provided" is intended to mean that at least one of the arylene groups in formula (A) is substituted with at least one R. For example, when m=1, the only arylene group in formula (A) is (R), where n is 1 to 4. n and when m=2 or 3, at least one of the arylene groups in formula (A) is (R) where n is 1 to 4. n is a phenyl substituted with

[0030] According to one embodiment, when m=2 or 3, all arylene groups of formula (A) have n=1 to 4 (R n is a phenyl substituted with

[0031] More specifically, n may be 1.

[0032] Unless otherwise indicated, bonds not connected to a particular carbon in the aromatic groups described herein are not limited with respect to their position on the aromatic ring. According to one embodiment, in formula (A), the bond is in the para position.

[0033] Ar is preferably represented by the following formula (A1): [ka] (Each occurrence of R in formula (A) or (A1) is selected from the group consisting of C3-C8 spiro-substituted cycloaliphatic groups, -NO2, -CN, -OH, and -(CH p X q ) r CH p X q’ wherein each occurrence of X is a halogen atom (typically F, Cl, Br, or I, more typically F or Cl), p and q are each integers from 0 to 2, p' and q' are each integers from 0 to 3, and r is an integer from 0 to 20, with the proviso that p+q=2, p'+q'=3, and q+q' is 1 or greater.

[0034] Each occurrence of R in formula (A) or (A1) can more specifically be selected from the group consisting of a C-C spiro substituted cycloaliphatic group, -NO, -CN, -OH, and -CX, and each occurrence of X is a halogen atom (typically F, Cl, Br, or I, more typically F or Cl).

[0035] R may more specifically be -CX3, where X is a halogen atom.

[0036] The repeat unit of formula (IV) is preferably of formula (IVa): [ka] It is expressed as:

[0037] Repeating unit (V) The polymer comprises a repeat unit of formula (V): [-O-Ar1-O-] (V) (Wherein, Ar1 is C6 to C 18 Arylene or -Ar c -L2-Ar d - and Ar c and Ar d are each independently C6 to C 18 arylene, and L2 is a divalent group selected from the group consisting of a bond, -O-, -S-, -SO-, SO2-, -(C=O)-, -(C=O)O-, -(C=O)NH-, -(C=S)S-, -CH=CH-, -C(CH3)2-, and -C(CF3)2-. The polymer also contains 10 to 35 mol %, and this ratio is based on the total molar amount of repeating units in the polymer.

[0038] This proportion may be preferably 10 to 25 mol %. This proportion may be advantageously 15 to 22 mol % or 10 to 20 mol %.

[0039] This proportion may be preferably 10.0 to 25.0 mol %. This proportion may be advantageously 15.0 to 22.0 mol % or 10.0 to 20.0 mol %.

[0040] According to one embodiment, Ar1 is [ka] is selected from the group consisting of Each occurrence of R in formula (B1) is selected from the group consisting of H, alkyl, typically C2-C8 alkyl; aryl, typically phenyl; cycloaliphatic, typically C3-C8 spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I; -NO2, -CN, -CX3 (X is halogen, typically F, Cl, Br, or I); or -OR. a (R a is H, alkyl, typically C2-C8 alkyl, more typically methyl or ethyl; and n is an integer from 0 to 4.

[0041] Preferably, n is 0.

[0042] According to a preferred embodiment, Ar1 is of the formula: [ka] and each occurrence of R in formula (B1) is selected from the group consisting of H, alkyl, typically C2-C8 alkyl; aryl, typically phenyl; cycloaliphatic, typically C3-C8 spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I; -NO2, -CN, -CX3 (wherein X is halogen, typically F, Cl, Br, or I); or -OR. a (R a is H, alkyl, typically C2 to C8 alkyl, more typically methyl or ethyl; and n is an integer from 0 to 4. Preferably, n is 0.

[0043] According to another embodiment, Ar1 is -Ar c -L2-Ar d - represented by; Ar in the formula c and Ar d are each independently [ka] is selected from the group consisting of Each occurrence of R in formula (B1) is selected from the group consisting of H, alkyl, typically C2-C8 alkyl; aryl, typically phenyl; cycloaliphatic, typically C3-C8 spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I, more typically F or Cl; -NO2, -CN, -CX3 (X is halogen, typically F, Cl, Br, or I); or -OR. a (R a is H, alkyl, typically C2-C8 alkyl, more typically methyl or ethyl; n is an integer from 0 to 4; L2 is a divalent group selected from the group consisting of a bond, -O-, -S-, SO2-, -(C=O)-, and -C(CF3)2-.

[0044] In the repeating unit of formula (V), Ar1 is -Ar c -L2-Ard According to the embodiment represented by -, L2 is preferably a bond, and Ar c and Ar d is preferably [ka] are expressed as Each occurrence of R in formula (B1) is selected from the group consisting of H, alkyl, typically C2-C8 alkyl; aryl, typically phenyl; cycloaliphatic, typically C3-C8 spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I, more typically F or Cl; -NO2, -CN, -CX3 (X is halogen, typically F, Cl, Br, or I); or -OR. a (R a is H, alkyl, typically C2 to C8 alkyl, more typically methyl or ethyl; and n is an integer from 0 to 4. Preferably, n is 0.

[0045] According to another preferred embodiment, Ar1 is: [ka] , -Ar c -L2-Ar d -, and (B1) and -Ar c -L2-Ar d - and in combination with L2 is preferably a bond, Ar c and Ar d is preferably [ka] are expressed as Each occurrence of R in formula (B1) is selected from the group consisting of H, alkyl, typically C2-C8 alkyl; aryl, typically phenyl; cycloaliphatic, typically C3-C8 spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I, more typically F or Cl; -NO2, -CN, -CX3 (X is halogen, typically F, Cl, Br, or I); or -OR. a(R a is H, alkyl, typically C2 to C8 alkyl, more typically methyl or ethyl; and n is an integer from 0 to 4. Preferably, n is 0.

[0046] The repeating units of formula (V) are more specifically derived from the following diols: hydroquinone, resorcinol, 4,4'-biphenol, 3,3'-biphenol, 2,4'-biphenol, 2,3'-biphenol, 3,4'-biphenol, isomers of dihydroxynaphthalenes, such as 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; isomers of dihydroxyanthracenes, such as 2,6-dihydroxyanthracene and 9,10-dihydroxyanthracene; and isomers of dihydroxyphenanthrene, such as 9,10-dihydroxyanthracene and 1,9-dihydroxyanthracene. More specifically, the repeat units of formula (V) are derived from the following diols: hydroquinone, resorcinol, 4,4'-biphenol, 3,3'-biphenol, 2,4'-biphenol, 2,3'-biphenol, and 3,4'-biphenol.

[0047] The repeating unit of formula (V) is preferably of formula (Va) and / or formula (Vb): [ka] It is of the following.

[0048] The repeating units of formula (V) may all be of formula (Va). The repeating units of formula (V) may all be of formula (Vb). The repeating units of formula (V) may all be a combination of repeating units of formulas (Va) and (Vb).

[0049] Repeating Unit (VI) The polymer may further comprise a repeat unit of formula (VI), [-OC-Ar2-CO-], where Ar2 is a C6-C 18It is an arylene group.

[0050] When repeat units of formula (VI) are present in the polymer according to the invention, their proportion may be from 0 mol % to 40 mol %, typically from 1 mol % to 35 mol %, said mol % being relative to the total molar amount of repeat units in the polymer.

[0051] Repeating unit (VII) The polymer of the present disclosure may further comprise a repeat unit of formula (VII) [-O-Ar3-CO-], where Ar3 is a C6 to C 18 An arylene group, the repeat unit of formula (VII) is different from the repeat units of formulae (I), (II), and (III).

[0052] When the repeat unit of formula (VII) is present in the polymer according to the present invention, its proportion may be from 0 mol % to 30 mol %, typically from 1 mol % to 30 mol %, said mol % being relative to the total molar amount of the repeat unit in the polymer.

[0053] According to a preferred embodiment (E1), the repeat units of the polymer consist essentially of or consist of repeat units of formula (I), repeat units of formula (IV), repeat units of formula (V) and optionally repeat units of formula (II) and / or (III). According to this embodiment (E1), the repeat units of formula (V) are more particularly repeat units of formula (Va) and / or (Vb).

[0054] According to a preferred embodiment (E2), particularly applicable to embodiment (E1), the proportion of repeat units in the polymer is repeating unit (I), or a combination of repeating unit (I) with repeating units (II) and / or (III): 55 to 75 mol %, preferably 58 to 72 mol %, preferably 60 to 70 mol %; Repeating unit (IV): 10 to 25 mol %, preferably 15 to 22 mol %; Repeating unit (V): 10 to 25 mol %, preferably 15 to 22 mol % It is.

[0055] According to this embodiment (E2), these proportions are: Repeating unit (I), or a combination of repeating unit (I) and repeating unit (II) and / or (III): 55.0 to 75.0 mol %, preferably 58.0 to 72.0 mol %, preferably 60.0 to 70.0 mol %; Repeating unit (IV): 10.0 to 25.0 mol %, preferably 15.0 to 22.0 mol %; Repeating unit (V): 10.0 to 25.0 mol %, preferably 15.0 to 22.0 mol %. may be also possible.

[0056] More preferably, according to this embodiment (E2), these proportions are: repeating unit (I), or a combination of repeating unit (I) with repeating units (II) and / or (III): 58 to 72 mol % or 60 to 70 mol %; Repeating unit (IV): 15-22 mol%; Repeating unit (V): 15 to 22 mol% It is.

[0057] More preferably, according to this embodiment (E2), these proportions are: Repeating unit (I), or a combination of repeating unit (I) with repeating units (II) and / or (III): 58.0 to 72.0 mol % or 60.0 to 70.0 mol %; Repeating unit (IV): 15.0 to 22.0 mol%; Repeating units (V): 15.0 to 22.0 mol%. may be also possible.

[0058] In particular, the polymers of the present disclosure preferably have 30 mol % to 89 mol % of repeat units of formula (I), 1 mol % to 35 mol % of repeat units of formula (IV), and 10 mol % to 35 mol % of repeat units of formula (V), It consists of: The mole percent is based on the total molar amount of repeat units in the polymer.

[0059] In particular, the polymers of the present disclosure are further preferably at least 30 mol %, or at least 50 mol %, or at least 55 mol %, or at least 60 mol % of repeat units of formula (I) or a combination of repeat units of formula (I) with repeat units of formula (II) and / or (III); 5 mol % to 35 mol %, or 10 mol % to 25 mol %, or 10 mol % to 20 mol %, or 15 mol % to 20 mol % of repeat units of formula (IVa); and 10 mol % to 35 mol %, or 10 mol % to 25 mol %, or 10 mol % to 20 mol % of repeating units of formula (Va) and / or (Vb) It consists of: The mole percentages are based on the total molar amount of repeat units in the polymer.

[0060] Properties of the Polymers of the Invention The melting temperature (Tm) of the polymer is usually at least 255° C. The Tm is preferably at least 300° C., more preferably at least 350° C. In some embodiments, the Tm of the polymer is from 300° C. to 400° C., typically from 330° C. to 390° C.

[0061] A high Tm is beneficial in the microelectronics manufacturing space, as portable electronic device articles or components must survive assembly processing steps typically found in the space. Various lamination / surface mount technologies (SMT) use high temperatures, typically in excess of 260°C.

[0062] Tm is determined using differential scanning calorimetry (DSC) by methods and equipment known to those skilled in the art. More specifically, Tm can be determined by DSC, which consists of subjecting a sample of the polymer in powder form to cycles of heating, cooling, and heating at heating and cooling rates of 20° C. / min. mis determined using the maximum of the endothermic peak in the first heating cycle.

[0063] More specifically, the methods presented in the experimental section can be followed.

[0064] The Tg of the polymer is usually at least 150° C. The Tg is preferably higher than 160° C. The Tg is typically lower than 200° C. The Tg is typically between 160° C. and 180° C. The Tg is determined using differential scanning calorimetry (DSC) by using methods and equipment known to those skilled in the art.

[0065] Tg is determined using differential scanning calorimetry (DSC) by using methods and equipment known to those skilled in the art. More specifically, Tg can be determined by DSC, which consists of subjecting a sample of the polymer in powder form to cycles of heating, cooling, and heating at heating and cooling rates of 20° C. / min. T g is then determined as the inflection point of the transition in the second heating cycle.

[0066] More specifically, the methods presented in the experimental section can be followed.

[0067] A polymer can be characterized by its dielectric properties, in particular the dielectric constant (Dk or ε) and the dissipation factor (Df). The dielectric constant and dissipation factor can be determined using methods and equipment known to those skilled in the art. One suitable method for measuring the dielectric constant and dissipation factor of a mobile device article or component is to use a split cylinder resonator (SCR) according to the method described in IPC-TM-650 2.5.5.13. More specifically, the method for measuring the dielectric properties shown in the experimental section can be followed.

[0068] In one embodiment, the polymer is A dielectric constant ε(Dk) of 3.6 or less at 20 GHz, and / or Dissipation factor (Df) less than 0.0032 at 20 GHz, preferably less than 0.0020; where Dk and Df of the polymer are measured according to IPC-TM-650 2.5.5.13 when measured in the dry state, i.e., on the polymer film immediately after drying in an oven at 100° C. for 1 hour.

[0069] In another embodiment, the portable electronic device article or component comprises: A dielectric constant of 3.6 or less at 20 GHz, and / or Dissipation factor (Df) less than 0.0032 at 20 GHz, preferably less than 0.0030 where Dk and Df of the polymeric portable electronic device article or component are measured in wet condition, i.e., after immersion of a polymeric film in water at room temperature for 24 hours, in accordance with IPC-TM-650 2.5.5.13.

[0070] A portable electronic device article or part may exhibit the same values ​​of Dk and Df.

[0071] Preparation of the Polymers of the Invention The polymers of the present disclosure are prepared by polycondensation, which involves the use of the following monomers or acetylated monomers derived therefrom: Hydroxynaphthoic acid (HNA) (to obtain repeating unit (I)) alone or in combination with one or more hydroxybenzoic acids; Monomers of formula (IVb) [ka] (wherein Ar is as defined above); one or more diols of the formula HO-Ar1-OH, where Ar1 is as defined above.

[0072] Repeating units (I) are derived from 6-acetoxy-2-naphthoic acid (HNA). Repeating units of formula (II) or (III), when present in the polymers according to the invention, are derived from hydroxybenzoic acid monomers (4-hydroxybenzoic acid (4-HBA) and 3-hydroxybenzoic acid (3-HBA), respectively).

[0073] Monomers of formula (IVb) can be obtained from commercial sources or can be synthesized according to methods known to those skilled in the art. For example, trimellitic anhydride can be reacted with a diamine having the formula H2N-Ar-NH2, where Ar is as defined above. In one embodiment, the diamine is 2,2'-bis(trifluoromethyl)benzidine. The preparation of monomers of formula (IVb) can be according to the recipes shown in the experimental section.

[0074] The monomer of formula (IVb) preferably has the formula (IVc): [ka] The monomer may be:

[0075] The repeating unit of formula (V) is derived from a diol of formula HO-Ar1-OH, where Ar1 is as defined above. Exemplary diols include, but are not limited to, hydroquinone, resorcinol, 4,4'-biphenol, 3,3'-biphenol, 2,4'-biphenol, 2,3'-biphenol, 3,4'-biphenol, isomers of dihydroxynaphthalene, such as 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; isomers of dihydroxyanthracene, such as 2,6-dihydroxyanthracene and 9,10-dihydroxyanthracene; and isomers of dihydroxyphenanthrene, such as 9,10-dihydroxyanthracene and 1,9-dihydroxyanthracene.

[0076] The repeat unit of formula (VI), when present in the polymers of the present invention, is derived from a diacid of formula HOOC-Ar2-COOH, where Ar2 is as defined above. Exemplary diacids include, but are not limited to, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 3,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and 2,5-naphthalenedicarboxylic acid.

[0077] The repeat unit of formula (VII), when present in the polymer according to the invention, is derived from a hydroxycarboxylic acid monomer of formula HO-Ar3-COOH, where Ar3 is as defined above and is different from HNA, 4-HBA, and 3-HBA.

[0078] The monomers having a reactive -OH group may be acetylated (before or during polycondensation). Thus, the polycondensation may include 6-acetoxy-2-naphthoic acid as a monomer to obtain the repeat unit (I). Similarly, the diols may be acetylated (before or during polycondensation). Examples of acetylated diols are 1,3-phenylenediacetate (acetylated resorcinol) and / or 4,4'-diacetoxybiphenyl (acetylated 4,4'-biphenol). Thus, in one suitable method, the polymers are prepared by "preacetylation", in which these monomers are acetylated and isolated, followed by introduction of the acetylated monomers into the polycondensation reactor in which the polycondensation takes place. In another suitable method, the polymers are prepared by "in situ acetylation", in which these monomers are acetylated in the polycondensation reactor, followed by the subsequent polycondensation step in the same reactor.

[0079] The polycondensation is usually carried out at a temperature of at least 200° C. According to one embodiment, this temperature is increased stepwise. Examples of increasing the temperature at which the polycondensation is carried out are given in the experimental section. At the end of the polycondensation, the polymer can be recovered and dried.

[0080] The polymers of the present invention can be prepared according to the recipes given in the experimental section.

[0081] Polymer Composition In a second aspect, the present disclosure relates to a polymer composition comprising at least one polymer of the present invention and, optionally, at least one additive selected from the group consisting of fillers (including reinforcing agents), toughening agents, impact modifiers, plasticizers, colorants (e.g. pigments and / or dyes), surfactants, antistatic agents, lubricants, heat stabilizers, light stabilizers, flame retardants, anti-sag agents, nucleating agents, chain extenders, capping agents, laser light activatable compounds, thermally conductive fillers, dielectric modifiers, and antioxidants.

[0082] The proportion of additives present in the polymer composition is 20% by weight or less, 15% by weight or less, 10% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less, based on the total weight of the polymer composition; and / or at least 0.05 wt.-%, at least 0.1 wt.-%, at least 0.2 wt.-%, at least 0.3 wt.-%, at least 0.4 wt.-%, at least 0.5 wt.-%, at least 0.6 wt.-%, at least 0.7 wt.-%, or at least 0.8 wt.-%, based on the total weight of the polymer composition may be also possible.

[0083] The additives are typically blended with at least one polymer of the present invention to form a polymer composition. Blending can be conveniently performed by melt mixing the polymer and additives, for example using an extruder. Blending can also be performed by mixing the polymer and additives in a solvent and evaporating the solvent.

[0084] Some details about the additives that may be present in the polymer composition are now provided.

[0085] Filler The polymer composition may include at least one filler, which may generally be selected from mineral fillers (such as talc, mica, kaolin, calcium carbonate, calcium silicate, magnesium carbonate, etc.), boron nitride, zinc oxide, graphene, glass fibers, carbon fibers, synthetic polymer fibers, aramid fibers, aluminum fibers, titanium fibers, magnesium fibers, boron carbide fibers, rock wool fibers, steel fibers, and inosilicates (such as wollastonite).

[0086] The fillers may be conductive and non-conductive thermally conductive fillers such as boron nitride, zinc oxide, or graphene.

[0087] The filler ratio is 60% by weight or less, 55% by weight or less, 50% by weight or less, or 45% by weight or less, based on the total weight of the polymer composition; and / or At least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, or at least 25% by weight based on the total weight of the polymer composition may be also possible.

[0088] Preferably, the polymer composition does not contain more than 20% by weight (based on the total weight of the polymer composition) of additives.

[0089] The fillers (also called reinforcing fillers, including reinforcing agents) can be selected from fibrous and particulate reinforcing agents. Fibrous reinforcing fillers are considered herein to be materials having a length, width and thickness where the average length is significantly greater than both the width and thickness. Generally, such materials have an aspect ratio, defined as the average ratio between the length and the maximum width and thickness, of at least 5, at least 10, at least 20 or at least 50.

[0090] The filler may be, for example, a low dielectric constant fibrous filler, a hollow filler, a particulate filler, or the like.

[0091] The filler can be selected from the group of low dielectric constant fillers that exhibit a dielectric constant Dk less than 5.0 at frequencies from 1 megahertz (MHz) to 1 gigahertz (GHz) and a dissipation factor Df less than 0.002 at frequencies from 1 MHz to 1 GHz. Low dielectric constant particulate fillers include, but are not limited to, polymer particles such as PTFE particles, LCP particles, etc.

[0092] The filler may be selected from the group of glass fibers, advantageously exhibiting a Dk of less than 5.0 at frequencies from 1 MHz to 1 GHz and a Df of less than 0.002 at frequencies from 1 MHz to 1 GHz. Exemplary glass fibers include, but are not limited to, E-glass, S-glass, AR-glass, T-glass, D-glass, R-glass, or combinations thereof.

[0093] The shape and size of suitable glass fibers, such as low dielectric constant glass fibers, are not limited. The fibers may include crushed or chopped glass fibers. They may be in the form of whiskers or flakes. They may also be short glass fibers or long glass fibers. Glass fibers that may have a length of 4 mm (millimeters) or more are called long fibers, and fibers shorter than this are called short fibers. Glass fibers, such as low dielectric constant glass fibers, may have a circular, flat, or irregular cross section. Glass fibers with non-circular cross sections may be used. Alternatively, the glass fibers may have a circular cross section. The diameter of the glass fibers may be, for example, about 1 to about 15 μm. More specifically, the diameter of the low dielectric constant glass fibers may be, for example, about 4 to about 10 μm. Flat glass fibers, such as flat glass fibers (CSG 3PA-830) manufactured by Nitto Boseki Co., Ltd., may also be used.

[0094] Suitable fillers may be surface-treated with a surface treatment agent that includes a coupling agent to improve adhesion to polymer-based resins.Suitable coupling agents include, but are not limited to, silane-based coupling agents, titanate-based coupling agents, or mixtures thereof.Applicable silane-based coupling agents include aminosilanes, epoxysilanes, amidosilanes, and acrylic silanes.Organometallic coupling agents, such as titanium or zirconium-based organometallic compounds, may also be used.

[0095] The hollow filler may be, for example, hollow glass spheres, hollow glass fibers, or hollow ceramic spheres. Exemplary hollow glass spheres have a density of 0.2 grams per cubic centimeter (g / cm 3 )~0.6g / cm 3 Typically, suitable hollow glass spheres have a diameter of 5 μm to 50 μm.

[0096] Impact Modifier The polymer composition may comprise at least one impact modifier. Tougheners, also called impact modifiers, are generally natural or synthetic polymers with a low glass transition temperature (Tg), e.g., below room temperature, below 0° C., or even below −25° C. As a result of their low Tg, tougheners are typically elastomeric at room temperature.

[0097] The toughening agent can be a functionalized polymer backbone. For example, suitable toughening agents can be siloxane-based. The polymer backbone of the toughening agent can also be selected from elastomer backbones including polyethylene and its copolymers, such as ethylene-butene; ethylene-octene; polypropylene and its copolymers; polybutene; polyisoprene; ethylene-propylene-rubber (EPR); ethylene-propylene-diene monomer rubber (EPDM); ethylene-acrylate rubber; butadiene-acrylonitrile rubber, ethylene-acrylic acid (EAA), ethylene-vinyl acetate (EVA); acrylonitrile-butadiene-styrene rubber (ABS), block copolymer styrene ethylene butadiene styrene (SEBS); block copolymer styrene butadiene styrene (SBS); methacrylate-butadiene-styrene (MBS) type core-shell elastomers, or mixtures thereof.

[0098] When the toughening agent is functionalized, the functionalization of the backbone can occur by copolymerization of monomers containing the functionalization or by grafting the polymer backbone with additional components.

[0099] Notable examples of functionalized toughening agents are terpolymers of ethylene, acrylic esters and glycidyl methacrylate, copolymers of ethylene and butyl acrylic acid ester; copolymers of ethylene, butyl acrylic acid ester and glycidyl methacrylate; ethylene-maleic anhydride copolymers; EPR grafted with maleic anhydride; styrene copolymers grafted with maleic anhydride; SEBS copolymers grafted with maleic anhydride; styrene-acrylonitrile copolymers grafted with maleic anhydride; and ABS copolymers grafted with maleic anhydride.

[0100] Coloring agent The polymer composition may include at least one colorant. One or more colorants, such as pigments and / or dyes, may be particularly desirable additives in the polymer composition for producing white, black, or colored portable electronic device articles or components.

[0101] Laser Activatable Compounds The polymer composition may include at least one laser-activatable compound. The laser-activatable compound may be, for example, a spinel crystal-type filler. The spinel crystal-type filler may be, but is not necessarily, represented by the general formula: AB2O4, where A is typically a metal cation with a valence of 2 and is selected from the group including cadmium, chromium, manganese, nickel, zinc, copper, cobalt, iron, magnesium, tin, titanium, and combinations of two or more thereof, B is typically a metal cation with a valence of 3 and is selected from the group including chromium, iron, aluminum, nickel, manganese, tin, and combinations of two or more thereof, and O is primarily, but not necessarily, oxygen. Examples of suitable laser-activatable compounds may include titanium dioxide, aluminum nitride, or zirconium dioxide fillers.

[0102] The included polymeric compositions may also include other conventional additives commonly used in the art, such as plasticizers, colorants, pigments (e.g., black pigments such as carbon black and nigrosine), antistatic agents, dyes, lubricants (e.g., linear low density polyethylene, calcium or magnesium stearate, or sodium montanate), heat stabilizers, light stabilizers, flame retardants, nucleating agents, mold release agents, and antioxidants. Exemplary mold release agents include, but are not limited to, metal stearates, stearyl stearate, pentaerythritol tetrastearate, beeswax, montan wax, paraffin wax, and the like, or a combination comprising at least one of the foregoing mold release agents.

[0103] Solutions of polymers or polymer compositions In a third aspect, the present disclosure relates to a solution comprising the polymer described herein or the polymer composition described herein and a solvent.Surprisingly, it has been found that the polymer described herein is soluble in certain solvents.Therefore, the solution of the polymer described herein can be used to produce articles such as films by solution processing.

[0104] The suitable solvent is a polar organic solvent. In one embodiment, the solvent is selected from the group of polar organic solvents. The solvent can typically be selected from N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylpropylene urea (DMPU), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, dimethyl-2-methylglutarate, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, γ-butyrolactone, dihydrolevoglucosenone, phenol, substituted phenol, and mixtures thereof.

[0105] The proportion of the polymer in the solution is not particularly limited as long as it is soluble in the solvent. However, in one embodiment, the concentration of the polymer in the solution is 0.1 to 20%, typically 1 to 10%, more typically 2 to 5% by weight of the solution.

[0106] Uses of the polymers of the present invention In a fourth aspect, the present disclosure relates to a mobile device article or component comprising a polymer or polymer composition as described herein. In one embodiment, the mobile device article or component is in the form of a film for use as a dielectric insulating substrate, for example in a PCB or FPC.

[0107] The mobile device article or part can be manufactured according to any method known to those skilled in the art. Exemplary methods for manufacturing the mobile device article or part include, but are not limited to, injection molding, extrusion molding, compression molding, thermoforming, such as sheet thermoforming, vacuum forming, pressure molding, trap sheet molding, steam pressure molding, liquid resin casting, transfer molding, and additive manufacturing, such as 3D printing.

[0108] The polymer or polymer composition may also be injection molded for structural components of microelectronics and smart devices, portable electronic devices, i.e., electronic devices intended to be conveniently carried and used in a variety of locations. Portable electronic devices may include, but are not limited to, mobile phones, personal digital assistants ("PDAs"), laptop computers, tablet computers, wearable computing devices (e.g., smart watches, smart glasses, etc.), cameras, portable audio players, wireless audio devices, portable radios, global positioning system receivers, and portable game consoles.

[0109] The mobile device article or part may include, for example, a wireless antenna, which is an antenna capable of transmitting and receiving electromagnetic signals at radio frequencies, such as those suitable for cellular, WiFi, Bluetooth, and RFID communications. The mobile device article or part may be an antenna housing.

[0110] In some embodiments, the portable device article or part may be a mounting part having mounting holes or other fastening devices (including, but not limited to, a snap-fit ​​connector between itself and another part of the portable electronic device, including, but not limited to, a circuit board, a microphone, a speaker, a display, a battery, a cover, a housing, an electrical or electronic connector, a hinge, a wireless antenna, a switch, or a switch pad). In some embodiments, the portable electronic device may be at least a portion of an input device.

[0111] In some embodiments, the mobile device article or part is used in transportation, such as automobiles (e.g., smart cars / intelligent cars, e.g., those with 5G capabilities), aeronautical engineering articles, and drones.

[0112] In a fifth aspect, the present disclosure relates to a metal-clad laminate (La). The metal-clad laminate comprises a layer (L) made of or including a polymer or polymer composition as described herein. PC ) and layer (L PC ) with a metal foil (L M ) and

[0113] The metal is usually copper or stainless steel, preferably copper.

[0114] The copper foil may be a soft copper foil or an electrolytic copper foil.

[0115] Metal-clad laminates are made by applying a solution containing a polymer or a polymer composition to a metal foil (L M The material can be prepared by a process comprising the step of contacting a surface or a portion of a surface of the material.

[0116] In a sixth aspect, the present disclosure relates to the use of a solution as described herein for the manufacture of a film, or a portable electronics article or part, or for the manufacture of an automotive or aeronautical or drone article or part.

[0117] The solution of the present disclosure can be used to produce articles such as films by solution processing. The use of the solution in the production of varnishes and / or coatings, optionally including additives, is also envisioned. Suitable additives may be those described herein above and are selected from the group consisting of fillers (including reinforcing agents), toughening agents, impact modifiers, plasticizers, colorants, surfactants, pigments, antistatic agents, dyes, lubricants, heat stabilizers, light stabilizers, flame retardants, antisag agents, nucleating agents, chain extenders, crosslinking agents, capping agents, laser light activatable compounds, thermally conductive fillers, dielectric modifiers, and antioxidants. For example, low Df fillers, such as low Df particulate fillers, can be dispersed in the solution.

[0118] Suitable applications include depositing a layer of a solution described herein on a substrate, for example by casting, spray coating, spin coating, gravure coating, curtain coating, dip coating, slot die coating, inkjet printing, gravure printing, or screen printing, and removing the solvent from the layer. Typically, the solvent is removed from the layer by evaporating the solvent component of the layer. The substrate support layer may be exposed to elevated temperatures and / or reduced pressure to facilitate evaporation of the solvent. The substrate may be rigid or flexible and may include, for example, metal, polymer, glass, paper, or ceramic materials. For example, the substrate may be a thin copper foil having a surface roughness in the range of 2 to 15 μm, such as copper foil available from Advanced Copper Foil Inc.

[0119] The present invention is further illustrated in the following non-limiting examples. EXAMPLES

[0120] Experimental Section Example 1. Synthesis of 2,2'-(2,2'-bis(trifluoromethyl)-[1,1'-biphenyl]-4,4'-diyl)bis(1,3-dioxoisoindoline-5-carboxylic acid) ("Im-C12 Monomer") An oven-dried 2 L, 2-neck round bottom flask equipped with a Dean-Stark trap, reflux condenser, nitrogen inlet and outlet, and magnetic stir bar was charged with 2,2'-bis(trifluoromethyl)benzidine (52.07 g, 0.16 mol) and anhydrous NMP (342 mL, 12.9 wt % solution in NMP). The 2,2'-bis(trifluoromethyl)benzidine was dissolved in NMP at room temperature. Once dissolved, trimellitic anhydride (62.47 g, 0.32 mol) was added to the reaction and stirred at room temperature for 16 hours to give a clear, pale yellow / brown solution. After 16 hours, toluene (60 mL) was added to the reaction mixture and the solution was heated to 165° C. The reaction was followed by observation of the water content in the Dean-Stark trap and by thin layer chromatography (TLC). After 5 hours at 165° C., the reaction was judged to be complete. The pale yellow homogeneous solution was allowed to cool to room temperature under a continuous stream of N2. The product was precipitated by adding deionized water (600 mL) and stirring for 30 min. The white precipitate was collected by vacuum filtration, transferred to a 2 L Erlenmeyer flask, and washed three times with deionized water (1,000 mL per wash) by stirring at room temperature for 30 min. The product was placed in a vacuum oven at 100°C and 30 mmHg (absolute) for 48 h to give 120.22 g of Im-C12 product as a white solid with residual NMP remaining.

[0121] Example 2. Synthesis of PEI and preparation of PEI films Several PEI polymers were synthesized by polycondensation of HNA, Im-C12, and one or more diols. The following procedure is specific to the synthesis of one of the polymers, polymer A, but is representative of all polymers prepared. Those skilled in the art will understand that parameters such as hold times at various temperatures and final pressure in the reactor can be varied.

[0122] The reaction was carried out in a dry 100 mL round bottom flask as a reactor equipped with an overhead stirrer, a nitrogen inlet, and a distillation nozzle attached to the receiver flask. The PEI polymer was prepared using preacetylated monomers introduced into the melt polymerization reactor (flask) where the polycondensation took place. Under N2 flow, 11.7727 g (60 mol%) of 6-acetoxy-2-naphthoic acid (preacetylated HNA), 11.4044 g (20 mol%) of Im-C12, 1.6617 g (10 mol%) of 1,3-phenylenediacetate (preacetylated resorcinol), and 2.3061 g (10 mol%) of 4,4'-diacetoxybiphenyl (preacetylated 4,4'-biphenol) were placed in the flask. Subsequent vacuum degassing and N2 gas purging (three times) ensured an oxygen-free environment. The flask was then flushed with N2 and visualized by bubbling with a mineral oil bubbler. The flask was then immersed in a bismuth:tin alloy bath (58:42 w / w ratio) preheated to 240°C and held for 25 minutes to initiate the melting of the monomers. The temperature was then increased to 245°C and held for an additional 10 minutes. The temperature of the reaction mixture was then increased to 270°C at a rate of 1°C / min and held at 270°C for 30 minutes to obtain a fully melted reaction mixture. The temperature was then increased to 320°C at a rate of 1°C / min and held for 10 minutes under flowing N2. The flow of N2 to the reactor was stopped and a slight vacuum (250-290 mmHg (absolute)) was applied for 10 minutes to facilitate the removal of acetic acid condensate, followed by a full vacuum reaching 2.5 mmHg (absolute). The reaction was held under high vacuum until no significant condensate was observed coming out of the reaction and the polymer sample had solidified around the stirring blade, typically 1.5-2 hours, after which the sample was cooled under a stream of N2 and removed from the stirring blade.

[0123] [Table 1]

[0124] Preparation of PEI films The films were made by compression molding. Compression molding utilized two stainless steel plates layered with Kapton film and aluminum shims to control thickness (0.0015 inches). The sandwich was placed in the center of the press and heated without pressure for 2 minutes to bring the temperature up. After the first heating step, the upper platen was brought into contact with the sandwich and pressure was applied with the following cycle: apply 2 tons of force for 0.75 minutes, release, apply 2 tons of force for 0.75 minutes, release. The sandwich was quickly removed from the press and allowed to cool on the bench. The PEI film was then removed from the sandwich and placed in an inert N2 oven and annealed at 300°C for 16 hours.

[0125] Example 3. Thermal, dielectric, and solubility properties of PEI of the present invention The thermal, dielectric, and solubility properties of the PEI produced according to Example 2 were evaluated as follows.

[0126] Measurement method for glass transition temperature (Tg) and melting point (Tm)

[0127] [Table 2]

[0128] DSC equipment used: TA Instruments Q20-2DSC, calibrated using indium (MP = 156.60 °C), N2 gas flow rate maintained at 50 mL / min.

[0129] Measurement method for dielectric properties (Dk and Df)

[0130] [Table 3]

[0131] Split cylinder resonator used: KEAD 20GHz SCR operating at 20GHz.

[0132] Solubility test used Solubility testing was performed by placing 5 wt% of the cryogenically ground polymer powder in a vial and adding 95 wt% N-methyl-2-pyrrolidone (NMP). The samples were then heated at 150°C for 6 hours. For samples that showed small amounts of particles, the solution was passed through a bed of Celite. For samples that showed large amounts of particles, no filtration was performed. The samples were then cooled to room temperature overnight and evaluated for particles the next day.

[0133] The results are reported as follows: ++ no particles when heated for 6 hours and after cooling, + some particles when heated and none after filtering and cooling, - some particles when heated and particles after filtering and cooling, -- no or very little solubility after heating. The thermal, dielectric, and solubility properties of the PEI polymers of the present invention are summarized in Table 2 below:

[0134] [Table 4]

[0135] As shown in Table 2, PEI polymers A-E exhibit a unique combination of solubility and dielectric performance that makes them useful in a variety of applications, including articles and components of portable electronic devices.

[0136] Example 4. Effect of humidity on PEI The effect of humidity on the dielectric constant and dielectric loss tangent of PEI was also evaluated. The dielectric properties were measured either immediately after drying in an oven at 100 °C for 0.5-1 h or after immersion in water at room temperature for 24 h and are denoted as "dry" and "wet", respectively. Microwave dielectric properties were measured according to IPC-TM-650 2.5.5.13 using a split cylinder resonator (KEAD 20 GHz SCR) operating at 20 GHz. For commercial polyimide (PI) Cu clad laminates (CCL), the Cu layer was chemically etched away according to the procedure specified in IPC-TM-650 2.3.7. The results are summarized in Table 3 below.

[0137] [Table 5]

[0138] As shown in Table 3, PEI (polymers A to E) had a ΔDf (Df wet -Df dry As expressed in ΔDf values, PEI A-E did not show a significant increase in Df after 24 hours of water immersion compared to the commercial PI, which had ΔDf values ​​of 0.0078 and 0.0065. The data in this table also show that PEI A-E had superior (much lower) absolute Df values ​​at 20 GHz than the commercial PI, even after equilibration in water.

Claims

1. A repeating unit of formula (I) or a combination of a repeating unit of formula (I) with a repeating unit selected from the group consisting of repeating units of formulas (II), (III) and combinations thereof: 【Chemistry 1】 at least 30 mol % of Repeating units of formula (IV): 【Chemistry 2】 (Wherein, Ar is 【Transformation 3】 (In the formula, Each entity in R is C ３ ~C ８ Spiro-substituted cycloaliphatic groups, —NO ２ , —CN, —OH, or a haloalkyl group; m is an integer from 1 to 3, each occurrence of n is an integer from 0 to 4, provided that at least one occurrence of n is an integer from 1 to 4 【Chemistry 4】 selected from the group consisting of 1 mol % to 35 mol % of Repeating units of formula (V): [-O-Ar １ -O-] (V) (In the formula, Ar １ is C ６ ~C １８ Arylene or -Ar ｃ -L ２ -Ar ｄ - and In the formula, Ar ｃ and Ar ｄ are each independently C ６ ~C １８ arylene, and L ２ represents a bond, -O-, -S-, -SO-, SO ２ -, -(C=O)-, -(C=O)O-, -(C=O)NH-, -(C=S)S-, -CH=CH-, -C(CH ３ ) ２ -, and -C(CF ３ ) ２ - is a divalent group selected from the group consisting of 10 to 35 mol % of A polymer comprising: A polymer wherein said mole percent is relative to the total molar amount of repeat units in said polymer.

2. 2. The polymer according to claim 1, wherein the proportion of repeating units (I) or the proportion of a combination of repeating units of formula (I) and repeating units selected from the group consisting of repeating units of formulas (II), (III), and combinations thereof is 50 to 80 mol %, or 55 to 75 mol %, or 60 to 70 mol %.

3. 2. The polymer according to claim 1, wherein the proportion of repeating units (I) or the proportion of a combination of repeating units of formula (I) and repeating units selected from the group consisting of repeating units of formulas (II), (III), and combinations thereof is 58 to 72 mol %.

4. 2. The polymer according to claim 1, wherein the proportion of repeating units (IV) is 5 to 35 mol % or 10 to 25 mol %.

5. 2. The polymer according to claim 1, wherein the proportion of repeating units (IV) is 15 to 22 mol %.

6. 2. The polymer according to claim 1, wherein the proportion of repeating units (V) is 10 to 25 mol % or 15 to 22 mol %.

7. at least 30 mol % of repeat units of formula (I); 1 mol % to 35 mol % of repeating units of formula (IV), preferably formula (IVa); 10 mol % to 35 mol % of at least one repeating unit of formula (V) 2. The polymer of claim 1, comprising:

8. The following percentages: Repeating unit (I) or a combination of repeating unit (I) with repeating units (II) and / or (III): 55 to 75 mol %, preferably 58 to 72 mol %, preferably 60 to 70 mol %; Repeating unit (IV): 10 to 25 mol %, preferably 15 to 22 mol %; Repeating unit (V): 10 to 25 mol %, preferably 15 to 22 mol % 2. The polymer of claim 1 having the formula:

9. The following percentages: Repeating unit (I), or a combination of repeating unit (I) with repeating units (II) and / or (III): 58 to 72 mol % or 60 to 70 mol %; Repeating unit (IV): 15 to 22 mol%; Repeating unit (V): 15 to 22 mol%; 2. The polymer of claim 1 having the formula:

10. Ar is a group represented by formula (A1): 【Transformation 5】 The polymer according to claim 1 ,

11. Each occurrence of R in formula (A) or (A1) is C ３ ~C ８ Spiro-substituted cycloaliphatic groups, —NO ２ , -CN, -OH, and -(CH ｐ X ｑ ) ｒ CH ｐ X ｑ’ wherein each occurrence of X is a halogen atom (typically F, Cl, Br, or I, more typically F or Cl), p and q are each integers from 0 to 2, p' and q' are each integers from 0 to 3, r is an integer from 0 to 20, and wherein p+q=2, p'+q'=3, and q+q' is greater than or equal to 1.

12. Each occurrence of R in formula (A) or (A1) is C ３ ~C ８ Spiro-substituted cycloaliphatic groups, —NO ２ , —CN, —OH, and —CX ３ and each occurrence of X is a halogen atom (typically F, Cl, Br, or I, more typically F or Cl).

13. R is -CF ３ 11. The polymer of claim 10, wherein:

14. The repeating unit of formula (IV) is represented by formula (IVa): 【Transformation 6】 2. The polymer of claim 1, wherein

15. Ar １ but, 【Transformation 7】 wherein each occurrence of R is H, alkyl, typically C ２ ~C ８ Alkyl; aryl, typically phenyl; cycloaliphatic, typically C ３ ~C ８ Spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I; —NO ２ , -CN, -CX ３ (X is a halogen, typically F, Cl, Br, or I); or -OR ａ (R ａ is H, alkyl, typically C ２ ~C ８ alkyl, more typically methyl or ethyl; and n is an integer from 0 to 4.

2. The polymer of claim 1 selected from the group consisting of:

16. Ar １ but, 【Transformation 8】 wherein each occurrence of R is H, alkyl, typically C ２ ~C ８ Alkyl; aryl, typically phenyl; cycloaliphatic, typically C ３ ~C ８ Spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I; —NO ２ , -CN, -CX ３ (X is a halogen, typically F, Cl, Br, or I); or -OR ａ (R ａ is H, alkyl, typically C ２ ~C ８ alkyl, more typically methyl or ethyl; and n is an integer from 0 to 4.

2. The polymer of claim 1, wherein:

17. Ar １ Ga-Ar ｃ -L ２ -Ar ｄ - and Ar ｃ and Ar ｄ However, each independently, 【Chemistry 9】 wherein each occurrence of R is H, alkyl, typically C ２ ~C ８ Alkyl; aryl, typically phenyl; cycloaliphatic, typically C ３ ~C ８ spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I, more typically F or Cl; —NO ２ , -CN, -CX ３ (X is a halogen, typically F, Cl, Br, or I); or -OR ａ (R ａ is H, alkyl, typically C ２ ~C ８ alkyl, more typically methyl or ethyl); n is an integer from 0 to 4; L ２ represents a bond, —O—, —S—, or —SO ２ -, -(C=O)-, and -C(CF ３ ) ２ - is a divalent group selected from the group consisting of 2. The polymer of claim 1 selected from the group consisting of:

18. Ar ｃ and Ar ｄ However, 【Chemistry 10】 wherein each occurrence of R is H, alkyl, typically C ２ ~C ８ Alkyl; aryl, typically phenyl; cycloaliphatic, typically C ３ ~C ８ spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I, more typically F or Cl; —NO ２ , -CN, -CX ３ (X is a halogen, typically F, Cl, Br, or I); or -OR ａ (R ａ is H, alkyl, typically C ２ ~C ８ alkyl, more typically methyl or ethyl); n is an integer from 0 to 4; L ２ is a bond) 18. The polymer of claim 17, wherein:

19. Ar １ but, 【Chemistry 11】 , -Ar ｃ -L ２ -Ar ｄ -, and (B1) and -Ar ｃ -L ２ -Ar ｄ - and in combination with L ２ is preferably a bond, and Ar ｃ and Ar ｄ is preferably 【Chemistry 12】 (Each occurrence of R in formula (B1) is H, alkyl, typically C ２ ~C ８ Alkyl; aryl, typically phenyl; cycloaliphatic, typically C ３ ~C ８ spiro-substituted cycloaliphatic; halogen, typically F, Cl, Br, or I, more typically F or Cl; —NO ２ , -CN, -CX ３ (X is a halogen, typically F, Cl, Br, or I); or -OR ａ (R ａ is H, alkyl, typically C ２ ~C ８ alkyl, more typically methyl or ethyl; n is an integer from 0 to 4, preferably n is 0.

2. The polymer of claim 1, wherein each of the

20. The repeating unit of formula (V) is represented by formula (Va) and / or formula (Vb): 【Chemistry 13】 2. The polymer of claim 1, wherein

21. The repeating unit of formula (VI) [—OC-Ar ２ -CO-] (wherein, Ar ２ are each independently C ６ ~C １８ 10. The polymer of claim 1 further comprising an arylene group.

22. The repeating unit of formula (VII) [—O—Ar ３ -CO-] (wherein, Ar ３ is a C different from the repeating units of formulas (I), (II), and (III). ６ ~C １８ 10. The polymer of claim 1 further comprising an arylene group.

23. 23. A polymer according to claim 21 or claim 22, wherein the proportion of repeat units of formula (VI) is from 0 mol % to 40 mol %, typically from 1 mol % to 35 mol %, said mol % being relative to the total molar amount of repeat units in the polymer, and / or the proportion of repeat units of formula (VII) is from 0 mol % to 30 mol %, typically from 1 mol % to 30 mol %, said mol % being relative to the total molar amount of repeat units in the polymer.

24. 2. The polymer of claim 1, wherein the repeat units of the polymer consist essentially of or consist of repeat units of formula (I), repeat units of formula (IV), in particular repeat units of formula (IVa), repeat units of formula (V), and optionally repeat units of formula (II) and / or (III).

25. The ratio of the repeating units is Repeating unit (I) or a combination of repeating unit (I) with repeating units (II) and / or (III): 55 to 75 mol %, preferably 58 to 72 mol %, preferably 60 to 70 mol %; Repeating unit (IV): 10 to 25 mol %, preferably 15 to 22 mol %; Repeating unit (V): 10 to 25 mol %, preferably 15 to 22 mol % 25. The polymer of claim 24, wherein:

26. The ratio of the repeating units is Repeating unit (I), or a combination of repeating unit (I) and repeating unit (II) and / or (III): 58.0 to 72.0 mol % or 60.0 to 70.0 mol %; Repeating unit (IV): 15.0 to 22.0 mol%; Repeating unit (V): 15.0 to 22.0 mol% 25. The polymer of claim 24, wherein:

27. exhibiting a melting point (Tm) of at least 255°C, Tm being determined by DSC in which a sample of said polymer in powder form is subjected to cycles of heating, cooling and heating at heating and cooling rates of 20°C / min; ｍ is determined using the maximum of the endothermic peak in the first heating cycle.

28. exhibiting a melting point (Tm) between 300°C and 400°C, more particularly between 330°C and 390°C, Tm being determined by DSC in which a sample of said polymer in powder form is subjected to cycles of heating, cooling and heating at a heating and cooling rate of 20°C / min; T ｍ is determined using the maximum of the endothermic peak in the first heating cycle.

29. exhibiting a glass transition temperature (Tg) of at least 150°C, Tg being determined by DSC in which a sample of said polymer in powder form is subjected to cycles of heating, cooling and heating at heating and cooling rates of 20°C / min; ｇ 10. The polymer of claim 1, wherein t is determined as the inflection point of the transition in the second heating cycle.

30. exhibiting a glass transition temperature (Tg) of less than 200°C, Tg being determined by DSC in which a sample of said polymer in powder form is subjected to cycles of heating, cooling and heating at heating and cooling rates of 20°C / min; ｇ 10. The polymer of claim 1, wherein t is determined as the inflection point of the transition in the second heating cycle.

31. It exhibits a glass transition temperature (Tg) of 160-180°C, Tg being determined by DSC in which a sample of said polymer in powder form is subjected to cycles of heating, cooling and heating at a heating and cooling rate of 20°C / min; T ｇ 10. The polymer of claim 1, wherein t is determined as the inflection point of the transition in the second heating cycle.

32. a dielectric constant ε (Dk) of 3.6 or less at 20 GHz, and / or a dissipation factor (Df) at 20 GHz of less than 0.0032, preferably less than 0.0020; 2. The polymer of claim 1, wherein the Dk and Df are measured on a film of the polymer immediately after drying in an oven at 100° C. for 1 hour according to IPC-TM-650 2.5.5.

13.

33. a dielectric constant ε (Dk) of 3.6 or less at 20 GHz, and / or A dissipation factor (Df) of less than 0.0032 at 20 GHz, preferably less than 0.0030 2. The polymer of claim 1, wherein the Dk and Df are measured according to IPC-TM-650 2.5.5.13 after immersion of a film of the polymer in water at room temperature for 24 hours.

34. exhibiting a ΔDf of less than 0.0015, preferably less than 0.0006, and ΔDf is expressed by the formula (Df ｗｅｔ -Df ｄｒｙ ) and Df ｗｅｔ and Df ｄｒｙ is the Df value measured in accordance with IPC-TM-650 2.5.5.13, and the Df ｄｒｙ is measured on a film of the polymer immediately after drying in an oven at 100°C for 1 hour, and ｗｅｔ 10. The polymer of claim 1, wherein the tensile strength is measured on a film of the polymer after immersion in water at room temperature for 24 hours.

35. 10. A polymer composition comprising at least one polymer according to claim 1 and, optionally, at least one additive selected from the group consisting of fillers (including reinforcing agents), tougheners, impact modifiers, plasticizers, colorants (e.g., pigments and / or dyes), surfactants, antistatic agents, lubricants, heat stabilizers, light stabilizers, flame retardants, anti-sag agents, nucleating agents, chain extenders, capping agents, laser light activatable compounds, thermally conductive fillers, dielectric modifiers, and antioxidants.

36. The proportion of the additive present in the polymer composition is 20% by weight or less, 15% by weight or less, 10% by weight or less, 7% by weight or less, 6% by weight or less, 5% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less, based on the total weight of the polymer composition; and / or at least 0.05 wt%, at least 0.1 wt%, at least 0.2 wt%, at least 0.3 wt%, at least 0.4 wt%, at least 0.5 wt%, at least 0.6 wt%, at least 0.7 wt%, or at least 0.8 wt%, based on the total weight of the polymer composition 36. The polymer composition of claim 35, wherein:

37. a dielectric constant ε (Dk) of 3.6 or less at 20 GHz, and / or a dissipation factor (Df) at 20 GHz of less than 0.0032, preferably less than 0.0020; 36. The polymer composition of claim 35, wherein the Dk and Df are measured on a film of the polymer composition immediately after drying in an oven at 100°C for 1 hour according to IPC-TM-650 2.5.5.

13.

38. a dielectric constant ε of 3.6 or less at 20 GHz, and / or A dissipation factor (Df) of less than 0.0032 at 20 GHz, preferably less than 0.0030 36. The polymer composition of claim 35, wherein the Dk and Df are measured according to IPC-TM-650 2.5.5.13 after immersion of a film of the polymer composition in water at room temperature for 24 hours.

39. ΔDf is less than 0.0015, preferably less than 0.0006, and ΔDf is expressed by the formula (Df ｗｅｔ -Df ｄｒｙ ) and Df ｗｅｔ and Df ｄｒｙ is the Df value measured in accordance with IPC-TM-650 2.5.5.13, and the Df ｄｒｙ is measured on a film of the polymer composition immediately after drying in an oven at 100°C for 1 hour, and ｗｅｔ 36. The polymer composition of claim 35, wherein the viscosity is measured on a film of the polymer after immersion in water at room temperature for 24 hours.

40. 36. A mobile device article or component comprising the polymer of claim 1 or the polymer composition of claim 35.

41. 41. The mobile device article or component of claim 40 in the form of a film.

42. a dielectric constant ε (Dk) of 3.6 or less at 20 GHz, and / or Dissipation factor (Df) less than 0.0032 at 20 GHz, typically less than 0.0030 41. The portable device article or part of claim 40, wherein the Dk and Df of the portable device article or part in a dry state are measured according to IPC-TM-650 2.5.5.

13.

43. a dielectric constant ε (Dk) of 3.6 or less at 20 GHz, and / or Dissipation factor (Df) less than 0.0032 at 20 GHz, typically less than 0.0030 41. The portable device article or part of claim 40, wherein the Dk and Df of the portable device article or part in a wet state are measured according to IPC-TM-650 2.5.5.

13.

44. A solution comprising the polymer of claim 1 and a solvent, or the polymer composition of claim 35 and a solvent.

45. 45. The solution of claim 44, wherein the solvent is a polar organic solvent, typically selected from N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylpropyleneurea (DMPU), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetonitrile, dimethyl-2-methylglutarate, methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate, dimethyl glutarate, dimethyl succinate, dimethyl adipate, γ-butyrolactone, dihydrolevoglucosenone, phenol, substituted phenols, and mixtures thereof.

46. 45. The solution of claim 44, wherein the concentration of the polymer in the solution is from 0.1 to 20%, typically from 1 to 10%, more typically from 2 to 5% by weight of the solution.

47. 45. Use of the solution of claim 44 for the manufacture of a film or portable electronic device article or component.

48. 45. Use of a solution according to claim 44 for the manufacture of automotive or aeronautical or drone articles or parts.

49. 45. Use of the solution according to claim 44 for the production of metal clad laminates.

50. A layer (L) made from or comprising the polymer of claim 1 or the polymer composition of claim 35. ＰＣ ) and the layer (L ＰＣ ) and a metal foil (L Ｍ ) and a metal-clad laminate (L ａ ).

51. The metal foil (L Ｍ 51. The metal clad laminate of claim 50, wherein the conductive layer is a copper foil.

Images