WO2023099178A1

WO2023099178A1 - Aromatic oligomers and polymers made therefrom

Info

Publication number: WO2023099178A1
Application number: PCT/EP2022/081782
Authority: WO
Inventors: Ryan MONDSCHEIN; Joel POLLINO; Kermit S. Kwan; David KERCHER; Valeriy KAPELYUSHKO
Original assignee: Solvay Specialty Polymers Usa, Llc
Priority date: 2021-11-30
Filing date: 2022-11-14
Publication date: 2023-06-08

Abstract

The present disclosure relates to new and inventive aromatic oligomers, including the use of such oligomers in the production of useful polymers. Such oligomers contain an aromatic core, flexible spacers, and reactive functionalities. The new and inventive oligomers enable the synthesis of useful polymers in various forms and by multiple processing techniques.

Description

AROMATIC OLIGOMERS AND POLYMERS MADE THEREFROM

Cross-reference to related applications

This application claims priority to US provisional application 63/284222 filed on 30 November 2021 , the whole content of this application being incorporated herein by reference for all purposes.

Field of the Disclosure

The present disclosure relates to new aromatic oligomers suitable for use in the production of useful polymers. Such oligomers comprise versatile functionality that enable the synthesis of useful polymers in various forms and by multiple processing techniques. The reaction of these new molecules with various difunctional comonomers can produce thermoplastic-like linear or branched polymers while homopolymerization or polymerization with multifunctional comonomers can produced crosslinked thermoset structures.

Background of the Disclosure

Polymeric materials, such as thermoplastic and thermoset materials, find applications in many industries, including the aviation, automotive, and marine industries. Such materials also find applications in the areas of health, medicine, and biotechnology, which is a rapidly developing domain based largely on known materials but moving to designed and engineered polymers, as well as information and communications, which is an emerging field for polymers significantly based on their electronic properties.

Articles and parts comprising polymeric materials are made by a variety of manufacturing processes, including, for example, extrusion, injection molding, thermoforming, liquid resin casting, additive manufacturing, such as 3D printing, and the like. However, there remains many challenges in the manufacturing of polymeric articles and parts. For example, one such challenge is that the nature of the polymeric material and the process used to manufacture articles and parts from it must be considered, as heating causes expansion, and the following cooling process can cause shrinkage and warping. These phenomena can affect the strength and integrity of the final product. Such features must also be balanced with the properties required for the product being made, such as mechanical and electrical properties, to name a few.

Thus, there is an ongoing need for new and improved compounds that can enable the production of useful polymeric materials, such as thermoplastics and thermosets, using a multitude of processing methods, such as, for example, extrusion, injection molding, thermoforming, liquid resin casting, additive manufacturing, such as 3D printing, etc. Herein, new and inventive oligomers, including the use of such oligomers in the production of useful polymers, are described.

Summary of the Invention

This objective, and others which will become apparent from the following detailed description, are met, in whole or in part, by the compounds, methods and/or processes of the present disclosure.

In a first aspect, the present disclosure relates to an oligomer represented by formula

wherein

An and Ar2 are each, independently, a C6-C14 arylene group or -Ar_a-L-Arb-, wherein Ar_a and Arb are each a C6-C14 arylene group and L is -(C=O)O-, - (C=S)O-, -(C=S)S-, -(C=O)NH-, -S-, -SO-, -SO2-, -O-, or -NH-;

A1, A2, and A3 are each, independently, -(CH2)m-, -(CH2CH2O)_PCH2CH2-, or - (S i R1 R2O)qSiRi R2-, wherein R1 and R2 are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20; R’ and R” are each, independently, -NRsRs, -OR7, -SRs, -(C=O)ORg,

wherein R4, Rs, and Re are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl;

R7, Rs, and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M⁺, wherein M⁺ is a monovalent cation; and n is an integer from 1 to 30. In a second aspect, the present disclosure relates to a process for producing the oligomer described herein, the process comprising: a) reacting a compound represented by formula II:

wherein

Ar is a C6-C14 arylene group or -Ar_a-L-Arb-, wherein Ar_a and Arb are each a C6-C14 arylene group and L is -(C=O)O-, -(C=S)O-, -(C=S)S-,-(C=O)NH-, - S-, -SO-, -SO2-, -O-, or -NH-;

R_a and Rb are each, independently H, alkyl, typically C1-C6 alkyl, more typically methyl, or M⁺, wherein M⁺ is a monovalent cation; with a compound represented by formula III:

HO-A-OH (III) wherein

A is -(CH₂)m- -(CH2CH₂O)_PCH2CH2- or -(SiRi R₂O)_qSiRi R₂-, wherein R1 and R₂ are each, independently, H or alkyl, typically C1-C6 alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20; and b) optionally, reacting the product of step a) with one or more reagents to convert one or more pendent hydroxyl groups into a moiety selected from the group consisting of -NRsRe, -OR7, -SRs, -(C=O)ORg,

R7 is alkyl, typically Ci-Ce alkyl, more typically methyl, or M⁺, wherein M⁺ is a monovalent cation;

Rs and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M⁺, wherein M⁺ is a monovalent cation.

In a third aspect, the present disclosure relates to a polymer comprising a repeating unit derived from the oligomer described herein or derived from the oligomer produced by the process described herein.

In a fourth aspect, the present disclosure relates to a process for producing a polymer described herein, the process comprising: reacting the oligomer described herein or the oligomer produced by the process described herein with a compound comprising one or more, typically two or more, thiol or amine groups, with a compound comprising one or more acrylate or methacrylate groups, with a compound comprising one or more vinyl ether groups, or with a compound comprising one or more maleimide groups.

In a fifth aspect, the present disclosure relates to an article comprising the polymer described herein or polymer produced according to a process described herein.

Detailed Description

As used herein, the terms “a”, “an”, or “the” means “one or more” or “at least one” and may be used interchangeably, unless otherwise stated. As used herein, the term “and/or” used in a phrase in the form of “A and/or B” means A alone, B alone, or A and B together.

As used herein, the term “comprises” includes “consists essentially of” and “consists of.” The term “comprising” includes “consisting essentially of” and “consisting of.” “Comprising”, which is synonymous with “including,” “containing,” or “characterized by,” is intended to be inclusive or open-ended and does not exclude additional, unrecited elements or steps. The transitional phrase “consisting essentially of” is inclusive of the specified materials or steps and those that do not materially affect the basic characteristic or function of the composition, process, method, or article of manufacture described. The transitional phrase “consisting of” excludes any element, step, or component not specified.

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

As used herein, and unless otherwise indicated, the term “about” or “approximately” means an acceptable error for a particular value as determined by one of ordinary skill in the art, which depends in part on how the value is measured or determined.

In certain embodiments, the term “about” or “approximately” means within 1 , 2, 3, or 4 standard deviations. In certain embodiments, the term “about” or “approximately” means within 50%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1 %, 0.5%, or 0.05% of a given value or range.

Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10. Because the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values. Unless expressly indicated otherwise, the various numerical ranges specified in this application are approximations. Throughout the present disclosure, various publications may be incorporated by reference. Should the meaning of any language in such publications incorporated by reference conflict with the meaning of the language of the present disclosure, the meaning of the language of the present disclosure shall take precedence, unless otherwise indicated.

As used herein, the terminology "(Cx-Cy)" or “Cx-Cy” in reference to an organic group, wherein x and y are each integers, means that the group may contain from x carbon atoms to y carbon atoms per group.

As used herein, the term “aryl” refers to a 5- or 6-membered carbocyclic ring having a delocalized, conjugated IT system, with a number of IT electrons that is equal to 4n+2, where n is 0 or a positive integer, or an arrangement of 2 or more of such rings in which the rings are connected by bonds and/or share one or more sides, i.e. , are fused. One or more of the ring members may be a heteroatom, typically selected from oxygen, nitrogen, and sulfur, and one or more of the ring members may possess non-hydrogen substituents, typically selected from alkyl, alkoxyl, hydroxyalkyl, cycloalkyl, alkoxyalkyl, haloalkyl, aryl, alkaryl, and aralkyl. Exemplary aryl groups include, but are not limited to, those derived from benzene, biphenyl, furan, pyridine, imidazole, thiophene, acridine, cinnoline, quinoline, phenazine, naphthalene, anthracene, phenanthrene, acenaphthylene, pyrene, perylene, and the like.

The radicals described herein may be bivalent, i.e., two hydrogen atoms may be replaced by chemical bonds. Such groups are often modified by an “-ene” ending herein. For example, the term “alkylene” means an alkyl radical with an additional hydrogen replaced by a chemical bond. Similarly, the term “arylene” means an aryl radical with an additional hydrogen replaced by a chemical bond.

As used herein with reference to an organic compound, the term “aromatic” means that the organic compound comprises one or more aryl or arylene moieties as defined herein. Any substituent or radical described herein may optionally be substituted at one or more carbon atoms with one or more, same or different, substituents described herein. For instance, an aryl group may be further substituted with another aryl group or an alkyl group. Any substituent or radical described herein may also optionally be substituted at one or more carbon atoms with one or more substituents selected from the group consisting of halogen, such as, for example, F, Cl, Br, and I; nitro (NO2), cyano (CN), and hydroxy (OH).

In the first aspect, the present disclosure relates to an oligomer represented by formula I:

wherein

A1, A2, and A3 are each, independently, -(CH2)m-, -(CH2CH2O)_PCH2CH2-, or -

(S i R1 R2O)qSiRi R2-, wherein R1 and R2 are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20;

R’ and R” are each, independently, -NRsRe, -OR7, -SRs, -(C=O)ORg,

R7, Rs, and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M⁺, wherein M⁺ is a monovalent cation; and n is an integer from 1 to 30, typically 2 to 15.

An and Ar2 are each, independently, a Ce-Cu arylene group or -Ar_a-L-Arb-, wherein Ar_a and Arb are each a C6-C14 arylene group and L is -(C=O)O-, -(C=S)O-, -(C=S)S- -(C=O)NH-, -S-, -SO-, -SO2-, -O-, or -NH-. Suitable C6-C14 arylene groups include, but are not limited to, those derived from benzene, biphenyl, furan, pyridine, imidazole, thiophene, acridine, cinnoline, quinoline, phenazine, naphthalene, anthracene, phenanthrene, acenaphthylene, pyrene, perylene, and the like.

In an embodiment, An and Ar2 are each, independently, a C6-C14 arylene group, typically selected from the group consisting of those derived from benzene, naphthalene, biphenyl, anthracene, and phenanthrene.

In an embodiment, An and Ar2 are each, independently, selected from the group consisting of:

The two bonds connecting the carbonyl carbons to An and Ar2 are not limited and may be on the same ring or on different rings.

In another embodiment, An and Ar2 are each, independently, selected from the group consisting of:

In an embodiment, An and Ar2 are each, independently, a -Ar_a-L-Arb-, wherein Ar_a and Arb are each a C6-C14 arylene group and L is -(C=O)O-, -(C=S)O-, -(C=S)S-, - (C=O)NH-, -S-, -SO-, -SO2-, -O-, or -NH-. Suitable C6-C14 arylene groups are those described hereinabove.

In an embodiment, Ar_a and Arb are each, independently, selected from the group consisting of:

Ai, A2, and A3 provide functionalities that act as flexible spacers in polymers made from the oligomer of formula I. A1 , A2, and A3 are each, independently, -(CH2)m-, - (CH2CH2O)_PCH2CH2-, or -(SiRi R2O)_qSiRiR2-, wherein R1 and R2 are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20.

In an embodiment, A1 , A2, and A3 are each, independently, -(CH2)m-, wherein each occurrence of m is an integer from 5 to 20, typically 10 to 15.

In another embodiment, A1 , A2, and A3 are each, independently, - (CH2CH2O)_PCH2CH2-, wherein each occurrence of p is an integer from 2 to 10, typically 3 to 8.

In another embodiment, A1 , A2, and A3 are each, independently, -(SiRi R2O)_qSiRiR2-, wherein R1 and R2 are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, and each occurrence of q is an integer from 2 to 18.

In an embodiment, A1 , A2, and A3 are unsubstituted. R’ and R” provide the reactive functionality used for producing polymers from the oligomer of formula I. Suitable reactive moieties are -NRsRe, -OR?, -SRs, - (C=O)OR₉,

R7, Rs, and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M⁺, wherein M⁺ is a monovalent cation.

In an embodiment, R’ and R” are each, independently,

, wherein R4 is H or alkyl, typically Ci-Ce alkyl, more typically methyl.

In an embodiment, R’ and R” are each , wherein R4 is H or alkyl, typically C1-C6 alkyl, more typically methyl.

In the second aspect, the present disclosure relates to a process for producing the oligomer described herein, the process comprising: a) reacting a compound represented by formula II:

O O

R_aO - LI - Ar - U - QR_b

wherein

HO-A-OH (III) wherein

A is -(CH₂)m-, -(CH2CH2O)pCH₂CH2-, or -(SiRi R₂O)_qSiRi R2-, wherein R1 and R2 are each, independently, H or alkyl, typically C1-C6 alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20; and b) optionally, reacting the product of step a) with one or more reagents to convert one or more pendent hydroxyl groups into a moiety selected from the group consisting of -NRsRs, -OR7, -SRs, -(C=O)ORg,

The compound represented by formula II is an aromatic diacid, aromatic diester, or salt form thereof, in which Ar is a C6-C14 arylene group or -Ar_a-L-Arb-, wherein Ar_a and Arb are each a C6-C14 arylene group and L is -(C=O)O-, -(C=S)O-, -(C=S)S-,- (C=O)NH-, -S-, -SO-, -SO2-, -O-, or -NH-. Suitable C6-C14 arylene groups are those already described hereinabove. In an embodiment, Ar is a C6-C14 arylene group, typically selected from the group consisting of those derived from benzene, naphthalene, biphenyl, anthracene, and phenanthrene.

In an embodiment, Ar is selected from the group consisting of:

The two bonds connecting the carbonyl carbons to Ar are not limited and may be on the same ring or on different rings.

In another embodiment, Ar is selected from the group consisting of:

In an embodiment, Ar is -Ar_a-L-Arb-, wherein Ar_a and Arb are each a Ce-Cu arylene group and L is -(C=O)O-, -(C=S)O-, -(C=S)S-, -(C=O)NH-, -S-, -SO-, -SO2-, -O-, or - NH-. Suitable C6-C14 arylene groups are those described hereinabove.

The compound of formula II is reacted with a compound represented by formula III:

HO-A-OH (III) wherein

A is -(CH₂)m- -(CH2CH₂O)_PCH2CH2- or -(SiRi R₂O)_qSiRi R₂-, wherein Ri and R₂ are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20.

In an embodiment, A is -(CH₂)m-, wherein each occurrence of m is an integer from 5 to 20, typically 10 to 15. In this embodiment, the compounds of formula III are alkanediols. Suitable alkanediols include, but are not limited to, 1 ,2-ethanediol, 1 ,3- propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8- octanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,11 -undecanediol, 1 ,12-dodecanediol, and so on.

In another embodiment, A is -(CH₂CH2O)pCH₂CH2-, wherein each occurrence of p is an integer from 2 to 10, typically 3 to 8. In this embodiment, the compounds of formula III are polyethylene glycols produced from the polymerization of ethylene oxide. Suitable polyethylene glycols include, but are not limited to, diethylene glycol, triethylene glycol, tetraethylene glycol, and so on.

In yet another embodiment, A is -(SiRiR2O)_qSiRiR2-, wherein Ri and R2 are each, independently, H or alkyl, typically C1-C6 alkyl, more typically methyl, and each occurrence of q is an integer from 2 to 18. In this embodiment, the compounds of formula III are polysiloxanes. An exemplary polysiloxane is polydimethylsiloxane.

In an embodiment, A1 , A2, and A3 are unsubstituted.

The compounds of formula II and III may be obtained from commercial sources or synthesized according to published methods.

The reaction between the compound of formula II with the compound of formula III is an apparent transesterification reaction in which ester linkages are formed between the compound of formula II and the compound of formula III. Such reactions are known and may be conducted by to those of ordinary skill in the art according to known methods. However, in a favorable embodiment, the esterification reaction between the compound of formula II and the compound of formula III is conducted in the presence of a titanium compound, typically a titanium(IV) compound, more typically a titanium(IV) alkoxide. In a particular embodiment, titanium tetraisopropoxide is used. The reaction conditions are not particularly limited.

However, in an embodiment, the reaction is conducted at a temperature in the range of 150 °C to 250 °C, typically 200 °C to 240 °C. In an embodiment, the reaction is conducted under inert atmosphere and/or vacuum.

Optionally, the product from step a) of the process may be reacted with one or more reagents to convert one or more pendent hydroxyl groups into a moiety selected from the group consisting of -NRsRe, -OR7, -SRs, -(C=O)ORg,

In an embodiment, the product from step a) of the process is reacted with one or more reagents to convert one or more pendent hydroxyl groups into a moiety selected from the group consisting of

, or

, wherein R4 is H or alkyl, typically C1-C6 alkyl, more typically methyl.

In an embodiment, the product from step a) of the process is reacted with one or more reagents to convert one or more pendent hydroxyl groups into

, wherein R4 is H or alkyl, typically C1-C6 alkyl, more typically methyl.

Reactions for transforming hydroxyl groups into various functional groups are well- known to those of ordinary skill in the art. Such transformations are described in detail in March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, M. B. Smith and J. March, 5th Edition, John Wiley & Sons, 2001 , Comprehensive Organic Transformations, R. C. Larock, 2nd Edition, John Wiley & Sons, 1999, and Protecting Groups in Organic Synthesis, T. W. Greene and P. G. M. Wuts, 3rd edition, John Wiley & Sons, 1999, the entirety of each of which is hereby incorporated herein by reference.

In the third aspect, the present disclosure relates to a polymer comprising a repeating unit derived from the oligomer described herein or derived from the oligomer produced by the process described herein.

In an embodiment, the polymer comprises 1 to 100 %, typically 20 to 95 %, more typically 50 to 90 %, still more typically 65 to 80 %, by weight of the repeating unit derived from the oligomer described herein or derived from the oligomer produced by the process described herein, relative to the weight of the polymer. The polymer may be a thermoplastic or thermoplastic-like linear or branched polymer. In some cases, the polymer may be a thermoset or thermoset-like polymer, typically with crosslinked structure. In an embodiment, the polymer is a liquid crystalline polymer. As used herein, a liquid crystalline polymer, or “LCP”, refers to a type of thermoplastic polymer that exhibits properties between highly ordered solid crystalline materials and amorphous disordered liquids over a well-defined temperature range.

In the fourth aspect, the present disclosure relates to a process for producing a polymer described herein, the process comprising: reacting the oligomer described herein or the oligomer produced by the process described herein with a compound comprising one or more, typically two or more, thiol or amine groups, with a compound comprising one or more acrylate or methacrylate groups, with a compound comprising one or more vinyl ether groups, or with a compound comprising one or more maleimide groups.

The polymerization reaction may be carried out according to methods known to those of ordinary skill in the art.

In the fifth aspect, the present disclosure relates to an article comprising the polymer described hereinabove or polymer produced according to the process described hereinabove.

The article may be produced according to any method known to those of ordinary skill in the art, typically from the polymer or compositions comprising the polymer described herein. Exemplary methods for manufacturing the article include, but are not limited, injection molding, extrusion, compression molding, thermoforming, such as sheet thermoforming, vacuum forming, pressure forming, trapped sheet forming, steam pressure forming; liquid resin casting, transfer molding, and additive manufacturing, such as 3D printing.

The polymer or compositions comprising the polymer used to produce the articles described herein may further comprise optional materials, such as fibers, fillers, colorants, additives, and the like, that impart beneficial properties to the final article. Fibers may serve as reinforcing media and include, but are not limited to, carbon fiber, synthetic polymeric fibers, silicate fibers, such as aluminum silicate fibers, metal oxide fibers, such as alumina fibers, titania fibers, and magnesia fibers, wollastonite, rock wool fibers, silicon carbide fibers, etc. Exemplary polymeric fibers include fibers formed from high temperature engineering polymers such as, for example, poly(benzothiazole), poly(benzimidazole), polyarylates, poly(benzoxazole), polyaryl ethers and the like, and may include mixtures comprising two or more such fibers.

Other optional materials include glass, calcium silicate, silica, clays, such as kaolin, talc, chalk, mica, potassium titanate, and other mineral fillers; colorants, including pigments such as carbon black, titanium dioxide, zinc oxide, iron oxide, cadmium red, iron blue; and other additives such as alumina trihydrate, sodium aluminum carbonate, barium ferrite, etc.

Still further, the polymer or compositions comprising the polymer may further include additional additives commonly employed by those of ordinary skill in the art, such as thermal stabilizers, ultraviolet light stabilizers, oxidative stabilizers, plasticizers, lubricants, and mold release agents, such as polytetrafluoroethylene (PTFE) powder, and the like.

In an embodiment, the article is:

■ an injection molded article ;

■ an extruded article, such as a film, fiber, sheet stock, rod stock, tubing or profile ;

■ a compression molded article ;

■ a valve component or a related part thereof such as a seal ring ;

■ a compressor or a pump component;

■ a sealing component;

■ an electronic component;

■ a hard drive platter component, or a head component ;

■ a component useful in semi-conductor manufacturing;

■ a component of a semi-conductor test equipment;

■ a fitting and/or coupling of a fluid delivery system; ■ a matrix for structural continuous fiber composites ;

■ a cookware or bakeware;

■ a downhole abrasion tape or a flexible riser abrasion tape ;

■ an under-the-hood automotive component, that may be exposed to high heat ;

■ an article useful in lighting applications;

■ a thermally dissipative heat sink;

■ an aerospace electrical or electronic connector component or housing ;

■ a friction and wear component such as a bushing, a bearing or a thrust washer,

■ a gear ;

■ a mechanical drive component;

■ an electrical or electronic, wire or cable insulation or coating ;

■ a bushing, bearing or another frictional component of an elevator door component, or other sliding mechanism ; or

■ a bushing, bearing or another frictional component of a high temperature conveyor system;

■ a plate for turbo components and/or air induction ;

■ an hydraulic component, a seal, a poppet or a piston ring of an agricultural or construction equipment ;

■ an anti-wear layer of a push-pull cable ;

■ a glide ring, a tappet, a gear, an electronically driven pad, a control valve, a pump component, a bushing or a check ball of a brake system ;

■ a seal ring, a thrust washer, or a ball of a transmission component ;

■ a gear, a bushing or a bearing of a steering system component ;

■ a ramp button, a torque roller, a thrust button of a CVT (Continuous Variable transmissions) or clutch.

■ a pump component, a gear, or a sensor of an emission system ;

■ a pump or a G-rotor of an oil system ;

■ a swash plate of a compressor;

■ an air bag sensor;

■ a friction plate, a door sleeve or a bracket or another sliding component of a train door;

■ an automotive chassis component; or ■ a motor thrust washer or film for seat adjustment mechanisms.

In another embodiment, the article is:

■ a 3D-printed article;

■ a foam article;

■ a coating;

■ an adhesive or component of an adhesive;

■ a component of a composite article;

■ a component of a multi-layer article; or

■ a medical device component.

Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

The oligomers, polymers, methods and processes, and articles according to the present disclosure are further illustrated by the following non-limiting examples.

Example 1. Synthesis of an oligomer of formula I (NDA-TEG).

The reaction was performed in a dry two-neck 500-mL round-bottomed flask utilizing an overhead stirrer, nitrogen inlet, and distillation apparatus. 2,6- naphthalenedimethyl ester (24.35 g, 0.099 mol equiv), tetraethylene glycol (21.95 g, 0.113 mol equiv), and titanium tetraisopropoxide (catalytic, 50 uL) were introduced to a flask. Oxygen-free reaction conditions were achieved by subsequent degassing with vacuum and purging with N2 gas (3x). The reaction progressed at 200 °C for 1 hour, 1 °C/min ramp from 200 °C to 225 °C, 225 °C for 1 hour, 1 °C/min ramp from 225 °C to 235 °C, 235 °C for 1 hour, and lastly 235 °C for 1 hour under a vacuum of 75-100 mmHg at a constant stirring rate of 75 rpm and N2 gas purge. Methanol condensate was collected in a liquid nitrogen cooled round-bottomed flask. Once the oligomerization was completed, the reaction flask was cooled down to ambient temperature and a small aliqout was taken out for characterization, confirming the formation of the desired oligomer. The desired oligomer was characterized by nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and polarized optical microscopy (POM).

The resulting oligomer was then dissolved in 250 mL of dicholoroethane (15 wt%) and cooled down to 5 °C in an ice-water bath. Once the reaction flask was cooled, triethylamine (5.79 mL, 0.057 mol) was added and stirred for 1 hour. After an hour, acryloyl chloride (5.17 mL, 0.057 mol) was added dropwise over a period of 20 minutes and stirred for 24 hours. The cloudy solution was concentrated under reduced pressure to a solid. The resulting white solid was washed with 400 mL of cold deionized water (DI-H2O) to exhaust excess acryloyl chloride and dissolve salts. The white solid was collected by vacuum filtration and washed three times with 500 mL of cold DI-H2O. The resulting oligomer was placed to dry in a vacuum oven at room temperature (30 mmHg) for 48 hours.

Example 2. Synthesis of a compound of formula I (NDA-C12).

NDA-C12 was made according to the procedure of Example 1 , except that 1 ,12- dodecanediol was used instead of tetraethylene glycol.

Example 3. Synthesis of a compound of formula I (BB-TEG).

BB-TEG was made according to the procedure of Example 1 , except that 4,4’- biphenyldimethyl ester was used instead of 2,6-naphthalenedimethyl ester.

Claims

WHAT IS CLAIMED IS:

1 . An oligomer represented by formula I:

wherein

A1, A2, and A3 are each, independently, -(CH2)m-, -(CH2CH2O)_PCH2CH2-, or -

R’ and R” are each, independently, -NRsRe, -OR7, -SRs, -(C=O)ORg,

25

R7, Rs, and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M⁺, wherein M⁺ is a monovalent cation; and n is an integer from 1 to 30.

2. The oligomer according to claim 1 , wherein An and Ar2 are each, independently, selected from the group consisting of:

3. The oligomer according to claim 1 or 2, wherein An and Ar2 are each, independently, selected from the group consisting of:

4. The oligomer according to claim 1 , wherein An and Ar2 are each -Ar_a-L-Arb- wherein Ar_a and Arb are each, independently, selected from the group consisting of:

5. The oligomer according to any one of claims 1 -4, wherein A1 , A2, and A3 are each, independently, -(CH2)m-, wherein each occurrence of m is an integer from 5 to 20, typically 10 to 15.

6. The oligomer according to any one of claims 1 -4, wherein Ai , A2, and A3 are each, independently, -(CH2CH2O)_PCH2CH2-, wherein each occurrence of p is an integer from 2 to 10, typically 3 to 8.

7. The oligomer according to any one of claims 1 -6, wherein R’ and R” are each, independently,

, wherein R4 is H or alkyl, typically Ci-Ce alkyl, more typically methyl.

8. The oligomer according to any one of claims 1 -7, wherein n is an integer from 2 to 15.

9. A process for producing the oligomer according to any one of claims 1 -8, the process comprising: a) reacting a compound represented by formula II:

wherein

Ar is a C6-C14 arylene group or -Ar_a-L-Arb-, wherein Ar_a and Arb are each a C6-C14 arylene group and L is -(C=O)O-, -(C=S)O- -(C=S)S- -(C=O)NH- - S-, -SO-, -SO2-, -O-, or -NH-;

HO-A-OH (III) wherein

A is -(CH₂)m-, -(CH2CH2O)pCH₂CH2-, or -(SiRi R₂O)_qSiRi R₂-, wherein R1 and R₂ are each, independently, H or alkyl, typically C1-C6 alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20; and b) optionally, reacting the product of step a) with one or more reagents to convert one or more pendent hydroxyl groups into a moiety selected from the group consisting of -NR5R6, -OR7, -SRs, -(C=O)ORg,

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10. The process according to claim 9, wherein the step a) is conducted in the presence of a titanium compound, typically a titanium(IV) compound, more typically a titanium(IV) alkoxide.

11 . The process according to claim 9 or 10, wherein step a) is conducted at a temperature in the range of 150 °C to 250 °C, typically 200 °C to 240 °C.

12. The process according to any one of claims 9-11 , wherein step a) is conducted under inert atmosphere and/or vacuum.

13. A polymer comprising a repeating unit derived from the oligomer according to any one of claims 1 -8 or derived from the oligomer produced by the process according to any one of claims 9-12.

14. The polymer according to claim 13, wherein the polymer comprises 1 to 100 %, typically 20 to 95 %, more typically 50 to 90 %, still more typically 65 to 80 %, by weight of the repeating unit derived from the oligomer according to any one of claims 1 -8 or derived from the oligomer produced by the process according to any one of claims 9-12, relative to the weight of the polymer.

15. The polymer according to claim 13 or 14, wherein the polymer is a liquid crystalline polymer.

16. A process for producing a polymer according to any one of claims 13-15, the process comprising: reacting the oligomer according to any one of claims 1 -8 or the oligomer produced by the process according to any one of claims 9-12 with a compound comprising one or more, typically two or more, thiol or amine groups, with a compound comprising one or more acrylate or methacrylate groups, with a compound comprising one or more vinyl ether groups, or with a compound comprising one or more maleimide groups.

17. An article comprising the polymer according to any one of claims 13-15 or polymer produced according to claim 16.

18. The article according to claim 17, wherein the article is:

■ an injection molded article ;

■ an extruded article, such as a film, fiber, sheet stock, rod stock, tubing or profile;

■ a compression molded article;

■ a valve component or a related part thereof such as a seal ring;

■ a compressor or a pump component;

■ a sealing component;

■ an electronic component;

30 ■ a hard drive platter component, or a head component;

■ a component useful in semi-conductor manufacturing;

■ a component of a semi-conductor test equipment;

■ a fitting and/or coupling of a fluid delivery system;

■ a matrix for structural continuous fiber composites;

■ a cookware or bakeware;

■ a downhole abrasion tape or a flexible riser abrasion tape;

■ an under-the-hood automotive component, that may be exposed to high heat;

■ an article useful in lighting applications;

■ a thermally dissipative heat sink;

■ an aerospace electrical or electronic connector component or housing;

■ a gear;

■ a mechanical drive component;

■ an electrical or electronic, wire or cable insulation or coating;

■ a bushing, bearing or another frictional component of an elevator door component, or other sliding mechanism; or

■ a plate for turbo components and/or air induction;

■ an hydraulic component, a seal, a poppet or a piston ring of an agricultural or construction equipment;

■ an anti-wear layer of a push-pull cable;

■ a glide ring, a tappet, a gear, an electronically driven pad, a control valve, a pump component, a bushing or a check ball of a brake system;

■ a seal ring, a thrust washer, or a ball of a transmission component;

■ a gear, a bushing or a bearing of a steering system component;

■ a pump component, a gear, or a sensor of an emission system;

■ a pump or a G-rotor of an oil system;

■ a swash plate of a compressor;

31 ■ an air bag sensor;

■ an automotive chassis component; or

■ a motor thrust washer or film for seat adjustment mechanisms. The article according to claim 17, wherein the article is:

■ a 3D-printed article;

■ a foam article;

■ a coating;

■ an adhesive or component of an adhesive;

■ a component of a composite article;

■ a component of a multi-layer article; or

■ a medical device component.

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