US009 109080B2

(12) United States Patent (10) Patent No.: US 9,109,080 B2 Drake et al. (45) Date of Patent: *Aug. 18, 2015

(54) CROSS-LINKED ORGANIC POLYMER FOREIGN PATENT DOCUMENTS COMPOSITIONS AND METHODS FOR CONTROLLING CROSS-LINKING EP O251357 B1 1, 1988 REACTION RATE AND OF MODIFYING GB 2185114 7, 1987 SAME TO ENHANCE PROCESSABILITY (Continued) (71) Applicant: Delsper LP, Kulpsville, PA (US) OTHER PUBLICATIONS (72) Inventors: Kerry A. Drake, Red Hill, PA (US); Andrew F. Nordquist, Whitehall, PA Ladacki et al., “Studies of the Variations in Bond Dissociation Ener (US); Sudipto Das, Norristown, PA gies of Aromatic Compounds. I. Mono-bromo-aryles.” Proc. R. Soc. (US); William F. Burgoyne, Jr., Lond. a, r219, pp. 341-253 (1953). Bethlehem, PA (US); Le Song, Chalfont, (Continued) PA (US); Shawn P. Williams, North Wales, PA (US); Rodger K. Boland, Primary Examiner — Robert S. Loewe Levittown, PA (US) (74) Attorney, Agent, or Firm — Flaster/Greenberg P.C. (73) Assignee: Delsper LP, Kulpsville, PA (US) (*) Notice: Subject to any disclaimer, the term of this (57) ABSTRACT patent is extended or adjusted under 35 The invention includes a cross-linking composition compris U.S.C. 154(b) by 0 days. ing a cross-linking compound and a cross-linking reaction additive selected from an organic acid and/or an com This patent is Subject to a terminal dis pound, wherein the cross-linking compound has the structure claimer. according to formula (IV): (21) Appl. No.: 14/059,064 (22) Filed: Oct. 21, 2013 (IV) (65) Prior Publication Data US 2014/0284.850 A1 Sep. 25, 2014 Related U.S. Application Data (60) Provisional application No. 61/833,351, filed on Jun. ) A. 10, 2013, provisional application No. 61/716,800, filed on Oct. 22, 2012. (51) Int. Cl. () C08G 65/48 (2006.01) C08G 16/00 (2006.01) wherein the cross-linking reaction additive is capable of reacting with the cross-linking compound to form a reactive (Continued) oligomer intermediate, which is capable of cross-linking an (52) U.S. Cl. organic polymer. Also included is an organic polymer com CPC ...... C08G 65/00 (2013.01); C07C35/38 position for use in forming a cross-linked organic polymer, (2013.01); C07C 43/275 (2013.01); C08G comprising a cross-linking compound of Formula (IV), a 65/48 (2013.01); C08L 71/00 (2013.01) cross-linking reaction additive and at least one organic poly (58) Field of Classification Search mer. In one embodiment, the at least one organic polymer has None at least one halogen-containing reactive group and is dehalo See application file for complete search history. genated by reacting with an alkali metal compound. Methods for making Such compositions as well as articles of manufac (56) References Cited ture formed from Such methods and organic polymer compo sitions, wherein the compositions and methods control the U.S. PATENT DOCUMENTS cross-linking reaction rate of a crosslinking compound for 3,092,191 A 6, 1963 Austin et al. use in cross-linking an organic polymer are also included. 3,512,592 A 5, 1970 Kellner (Continued) 65 Claims, 7 Drawing Sheets

5.9 20.3 35.0 30.0, 35.0 fine (min) US 9,109,080 B2 Page 2

(51) Int. Cl. 2002/0195739 A1 12/2002 Bagley et al. C08G 65/00 2003, OO32339 A1 2/2003 Bell et al. (2006.01) 2005, 0161212 A1 7/2005 Leismer et al. C07C35/38 (2006.01) 2006, O19991.0 A1 9, 2006 Walton et al. C07C 43/275 (2006.01) 2007/O142547 A1 6/2007 Vaidya et al. COSL 7L/00 2007,0296.101 A1 12/2007 DiPietro et al. (2006.01) 2010/0022718 A1 1/2010 Tu et al...... 525/471 2010.0081007 A1 4/2010 Zheng et al. (56) References Cited 2010, 0126266 A1 5, 2010 Coenen 2011/O1394.66 A1 6, 2011 Chen et al. U.S. PATENT DOCUMENTS 2011/0260343 A1 10/2011 Burgoyne, Jr. et al. 2012fOO77935 A1 3/2012 Gurevich et al. 3,533,997 A * 10, 1970 Angelo ...... 525,436 2012fOO971.94 A1 4/2012 Mcdaniel et al. 4,609,714 A 9, 1986 Harris et al. 2012/010O379 A1 4/2012 Luo et al. 4,708,994 A 11, 1987 Wong 2012/0130041 A1* 5, 2012 Han et al...... 528,125 4,710,948 A 12, 1987 Withjack 2012fO252218 A1 10, 2012 Kori et al. 4,731,442 A 3, 1988 Lindley et al. 2013, OO12635 A1 1/2013 Ren et al. 4,827,761 A 5, 1989 Vinegar et al. 2013/0130529 A1* 5/2013 Ayers ...... 439,271 4,861,810 A 8, 1989 Dewhirst 2014/0213742 A1 7/2014 Drake et al. 5,108,840 A 4, 1992 Mercer 2014/0316079 A1 10/2014 Drake et al. 5,114,780 A 5, 1992 Mercer et al. 5,134,207 A 7, 1992 McGrath et al. FOREIGN PATENT DOCUMENTS 5,145,936 A 9, 1992 Mercer 5,155, 175 A * 10, 1992 Mercer et al...... 525/390 5,173,542 A 12, 1992 Lau et al. WO WOOO61667 A1 10, 2000 5,179,188 A 1, 1993 Mercer et al. WO WO 01/16232 A1 3, 2001 5,204,416 A 4, 1993 Mercer et al. WO WO 2009021999 A1 2, 2009 5,235,044 A 8, 1993 Mercer et al. WO WO 2010/O19488 A1 2, 2010 5,270,453 A 12, 1993 Lau et al. WO WO 2011071619 A2 6, 2011 5,658,994 A 8, 1997 Burgoyne, Jr. et al. WO WO 2013074120 A1 5, 2013 5,668.245 A 9, 1997 Marrocco, III et al. OTHER PUBLICATIONS 5,886, 130 A 3, 1999 Trimmer et al. 6,060, 170 A 5, 2000 Burgoyne, Jr. C.-M. Chan et al., “Crosslinking of Poly(arylene ether ketones). II. 6,184,284 B1 2, 2001 Stokich, Jr. et al. Crystallization Kinetics.” J. of Polymer Science: Part B: Polymer 6,339,966 B1 1, 2002 Kalidindi Physics, vol. 25, pp. 1655-1665 (1987). 6,582,251 B1 6, 2003 Burke et al. Hendrick, "Elastomeric behavior of Crosslinked poly(aryl ether 6,716,955 B2 4, 2004 Burgoyne, Jr. ketone)s at elevated temperatures.” Polymer, vol. 22, No. 23, pp. 6,855,774 B2 2, 2005 Kawasaki et al. 5094-5097, (1992). Butterworth-Heinimann Ltd. 6,878,778 B1 4, 2005 Kawasaki et al. Yi-Chi Chien et al., “Fate of Bromine in Pyrolysis of Printed Circuit 6,914,119 B2 7/2005 Yoshida et al. Board Wastes.” ChemoSphere, vol. 40, pp. 383-387 (2000). 7,001,678 B2 2, 2006 Casasabta, III et al. Burke et al., “High Pressure/High Temperature Technology and 7,087,701 B2 8, 2006 Londergan Introduction of LHT a New High Temperature Plastic.” MERL, 26 7,101,957 B2 9, 2006 Huang et al. pages (Sep. 2010). 7,109,249 B2 9, 2006 Bruza et al. Drake, “High Temperature Hybrid Elastomers.” PhD Thesis, (2011). 7,115,531 B2 10, 2006 Shaffer, II et al. 7,189,795 B2 3, 2007 Burgyyne, Jr. et al. International Search Report and Written Opinion for PCT/US 13/ 7,196,155 B2 3, 2007 Chen et al. 65977, mailed Apr. 17, 2014—15 pages. 7,249,971 B2 7/2007 Burke et al. International Search Report and Written Opinion for PCT/US14/ 7,307,137 B2 12/2007 Lau et al. 13246, mailed Apr. 30, 2014—16 pages. 7,589,228 B2 9, 2009 Nishichi et al. International Search Report and Written Opinion for PCT/US14/ 7,696,275 B2 4, 2010 Slay et al. 30666, mailed Aug. 13, 2014—19 pages. 7.919,825 B2 4, 2011 Kretz et al. Written Opinion for PCT/US14/30666, mailed Jan. 30, 2015–3 8,096.353 B2 1, 2012 Ver Meer pageS. 8,367,776 B2 2, 2013 Noguchi et al. 8,502.401 B2 8, 2013 Burgoyne, Jr. et al. * cited by examiner U.S. Patent Aug. 18, 2015 Sheet 1 of 7 US 9,109,080 B2

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F.G. 1 U.S. Patent Aug. 18, 2015 Sheet 2 of 7 US 9,109,080 B2

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(sa&ifieg) eleg o r 00:02,93666? US 9,109,080 B2 1. 2 CROSS-LINKED ORGANIC POLYMER International Patent Application Publication No. WO COMPOSITIONS AND METHODS FOR 2010/019488 A1, which is also assigned to the Applicant of CONTROLLING CROSS-LINKING the present application and is incorporated herein by refer REACTION RATE AND OF MODIFYING ence in relevant part, shows per(phenylethynyl) arene poly SAME TO ENHANCE PROCESSABILITY mers that are grafted to a second polymer to provide a cross linked polymeric network. CROSS-REFERENCE TO RELATED Previous attempts have also been made to control where APPLICATIONS SECTION crosslinks form along the backbone of high glass transition polymers to garner the desired mechanical properties and This application claims the benefit under 35 U.S.C. S 119 10 high temperature performance. U.S. Pat. No. 5,658.994, of (e) to U.S. Provisional Patent Applications Nos. 61/833,351, Applicant, incorporated herein by reference in relevant part, filed Jun. 10, 2013, entitled, “Cross-Linked Organic Polymer demonstrates the use of a poly(arylene ether) in low dielectric Compositions and Methods of Modifying Same to Enhance interlayers which may be cross-linked, for example, by cross Processability” and 61/716,800, filed Oct. 22, 2013, entitled: linking the polymer to itself, through exposure to tempera “Cross-Linked Organic Polymer Compositions and Methods 15 tures of greater than about 350° C. or alternatively by using a for Controlling Cross-Linking Reaction Rate for Forming the cross-linking agent. In this patent and as mentioned in U.S. Same.’ Pat. No. 5,874.516, cross-linking occurs at the ends of the polymer backbone using known end capping agents, such as BACKGROUND OF THE INVENTION phenylethynyl, benzocyclobutene, ethynyl, and nitrite. The degree of cross-linking can be limited with the results of a 1. Field of the Invention lower glass transition temperature, reduced chemical resis The present invention relates to cross-linked organic poly tance and lesser tensile strength. mers, including those having aromatic groups within the International Patent Application Publication No. WO polymer chain, and cross-linking compositions and methods 20130/74120 A1 of the Applicant of the present application, for making such polymers. More particularly, it relates to 25 also incorporated herein by reference in relevant part, dis methods for controlling the cross-linking reaction rate of the closes a cross-linking compound as used in the invention cross-linking compounds in Such compositions to form high described herein, which is blended with an uncrosslinked glass transition temperature organic polymers, and to meth polymer to achieve a crosslinked organic polymer with a ods for enhancing processability of such cross-linked organic higher glass transition temperature for use in extreme condi polymers and polymer compositions informing molded parts 30 tions such as in down-hole tool applications. which may be used, for example, in down-hole tool applica While cross-linking agents may be effective, there can be tions. difficulty in controlling the rate and extent of cross-linking. 2. Description of Related Art Cross-linked organic polymers having aromatic groups in the High glass transition temperature polymers have been use backbone such as cross-linked polyarylene ether polymers, ful for a number of high temperature applications. Modifica 35 including cross-linked polyetherether ketone (PEEK), even tion of such high glass transition organic polymers generally when made using agents to control cross-linking as described improves high temperature performance, strength and chemi herein are amorphous polymers that function well at high cal resistance for use as parts and articles of manufacture temperature (having a T above about 270° C.). The necessary in extreme temperature environments as compared crosslinking provides enhanced chemical resistance to add to to unmodified organic polymers. 40 the high temperature properties of the base polymers. Cross Cross-linking has been widely recognized as one way to linking can be done using techniques as noted in the patents modify high temperature polymeric materials. Several inven and patent application publications identified above and as tions have been aimed at improving the high temperature described herein using Applicant's techniques. In molding, performance of organic polymers, such as those having aro the controlled cross-linked polymers perform well at about matic groups in the backbone, by using cross-linking within 45 250° C. (or somewhat below the T of the materials). How the polymers by cross-linking to itself, grafting cross-linking ever, as molding temperatures rise, the reaction can accelerate compounds to the polymer, or incorporating cross-linking Such that full cure may be achieved in less than one minute. compounds into the polymer Such as by blending. Cycle times for injection molded articles, such as tubes, rods U.S. Pat. No. 5,874,516, which is assigned to the Applicant or electrical connectors, however, are generally three to five of the present application and is incorporated herein by ref 50 minutes or longer. A full cure in less than a minute can impede erence in relevant part, shows poly(arylene ether) polymers the usefulness of conventional molding techniques, such as that are thermally stable, have low dielectric constants, low injection molding or extrusion, in forming molded parts. moisture absorption and low moisture outgassing. The poly Prior art attempts to retard or inhibit and moderate cross mers further have a structure that may cross-link to itself or linking reactions using compounds and their reactions are can be cross-linked using a cross-linking agent. 55 known. See, Vanderbilt Rubber Handbook, 13th ed., 1990, p. U.S. Pat. No. 6,060,170, which is also assigned to the 281. However, there is still a need in the art to control and Applicant of the present application and is incorporated inhibit Such reactions, and to improve the ability to process herein by reference in relevant part, describes the use of Such polymers more easily using traditional molding tech poly(arylene ether) polymer compositions having aromatic niques. groups grafted on the polymer backbone, wherein the grafts 60 allow for cross-linking of the polymers in a temperature range BRIEF SUMMARY OF THE INVENTION of from about 200° C. to about 450° C. This patent discloses dissolving the polymer in an appropriate solvent for grafting The present invention includes a cross-linking composi the cross-linking group. Such required process steps can tion comprising a cross-linking compound and a cross-link Sometimes make grafting difficult or not practical in certain 65 ing reaction additive selected from an organic acid and/or an types of polymers or in certain polymeric structures, includ acetate compound, wherein the cross-linking compound has a ing, e.g., polyetherether ketone (PEEK). structure according to formula (IV): US 9,109,080 B2 4

-continued (IV)

wherein A is an arene moiety having a molecular weight of less than 10,000 g/mol, R' is selected from a group consisting of hydroxide (—OH), amine ( NH), halide, ether, ester, or amide, and x=2.0 to 6.0, wherein the cross-linking reaction additive is capable of reacting with the cross-linking com pound to form a reactive intermediate in the form of an oligomer, which reactive intermediate oligomer is capable of cross-linking an organic polymer. The cross-linking compound in the composition as noted above may have a structure according to the following:

The arene moiety of the cross-finking compound noted above preferably has a molecular weight of about 1,000 g/mol to about 9,000 g/mol, and more preferably about 2,000 g/mol to about 7,000 g/mol. One inhibitor that works well in crosslinking organic poly mers, particularly those with aromatic groups in the back 45 bone, and using a cross-linking compound Such as 9.9'-(bi phenyl-4,4'-diyl)bis(9H-fluoren-9-ol) shown in formula (I) below, may be, for example, in one embodiment herein, an organic acid Such as glacial acetic acid, formic acid, and/or benzoic acid. 50 (I) 55 ( ) ( )

60 Thus, in one embodiment, the cross-linking reaction addi tive is an organic acid which may be glacial acetic acid, formic acid, and/or benzoic acid. 65 In another embodiment, the cross-linking reaction additive may be an acetate compound that has a structure according to formula (II): US 9,109,080 B2 6 The cross-linking compound in this embodiment may have (II) the various structures noted above and the arene moiety may O also have the characteristics as noted above. In one embodiment of the invention, the cross-linking reac M-O ls CHR2 tion additive is an organic acid such as glacial acetic acid, wherein Misa Group I or a Group II metal; and R is an alkyl, formic acid and/or benzoic acid. In an alternative embodi aryl, or aralkyl group, wherein the alkyl group is a hydrocar ment of the invention, the cross-linking reaction additive is an bon group of 1 to about 30 carbon atoms, preferably about 1 acetate compound Such as those noted above having the struc to about 15 carbon atoms having 0 to about 10 ester or ether ture according to formula (II). More preferably, the acetate groups along or in the chain of the hydrocarbon group, pref 10 compound is one or more of hydrate, sodium erably about 0 to about 5 ester or ether groups, wherein R acetate, and/or , and salts and derivatives may have 0 to about 10, preferably about 0 to about 5, func thereof. The weight percentage ratio of the organic polymerto tional groups that may be one or more of sulfate, phosphate, the combined weight of the cross-linking compound and the hydroxyl, carbonyl, ester, halide, mercapto or potassium. cross-linking reaction additive in the composition of this More preferably, the acetate compound may be lithium 15 embodiment may be about 1:1 to about 100:1, and is prefer acetate hydrate, and/or potassium acetate, and ably about 3:1 to about 10:1. salts and derivatives thereof. The organic polymer composition may further comprise The weight percentage ratio of the cross-linking compound one or more additives. Preferably, the additive(s) is/are to the cross-linking reaction additive may be about 10:1 to selected from one or more of continuous or discontinuous, about 10,000:1, and more preferably about 20:1 to about long or short, reinforcing fibers selected from one or more of 1OOO:1. carbon fibers, glass fibers, woven glass fibers, woven carbon In another embodiment, the invention includes an organic fibers, aramid fibers, boron fibers, polytetrafluorethylene polymer composition for use in forming a cross-linked (PIPE) fibers, ceramic fibers, polyamide fibers, and/or one or organic polymer, comprising a cross-linking compound hav more filler(s) selected from carbon black, silicate, fiberglass, ing a structure as informula (IV) as described above; a cross 25 calcium Sulfate, boron, ceramic, polyamide, asbestos, fluo linking reaction additive selected from an organic acid and/or rographite, aluminum hydroxide, barium sulfate, calcium an acetate compound; and at least one organic polymer, wherein the cross-linking reaction additive is capable of carbonate, magnesium carbonate, silica, aluminum nitride, reacting with the cross-linking compound to form a reactive borax (sodium borate), activated carbon, pearlite, Zinc tereph intermediate in the form of an oligomer, which reactive inter thalate, graphite, talc, mica, silicon carbide whiskers or plate mediate oligomer is capable of cross-linking the organic 30 lets, nanofillers, molybdenum disulfide, fluoropolymer fill polymer. ers, carbon nanotubes and fullerene tubes. In a further embodiment, the invention includes an organic The additive preferably includes a reinforcing fiber which polymer composition for use in forming a cross-linked is a continuous or discontinuous, long or short fiber, that is organic polymer, comprising an organic polymer and a reac carbon fiber, polytetrafluoroethylene (PTFE) fiber, and/or tive cross-linking oligomer which is a reaction product of a 35 glass fiber. Most preferably, the additive is a reinforcing fiber cross-linking compound having a structure as informula (IV) is a continuous long fiber. The organic polymer composition described above and a cross-linking reaction additive selected in preferred embodiments comprises about 0.5% to about from an organic acid and/or an acetate compound. 65% by weight of additive(s) in the composition and more The organic polymer is preferably a polymer selected from preferably about 5.0% to about 40% by weight of additive(s) poly(arylene ether)s, polysulfones, polyetherSulfones, poly 40 in the composition. The organic polymer composition may imides, polyamides, polyureas, polyurethanes, polyphthala further comprise one or more of stabilizers, flame retardants, mides, polyamide-imides, poly(benzimidazole)s and pol pigments, colorants, plasticizers, Surfactants, and or dispers yaramids. antS. The organic polymer may also be a polymerin one embodi A method is also provided herein for controlling the cross ment herein that is a poly(arylene ether) including polymer 45 linking reaction rate of a cross-linking compound for use in repeating units along its backbone having the following struc cross-linking an organic polymer. The method comprises pro ture: viding a cross-linking composition comprising a cross-link ing compound and a cross-linking reaction additive selected from an organic acid and/or an acetate compound, wherein wherein Ar", Ari, Ar and Arare identical or different aryl 50 the cross-linking compound has a structure according to for radicals, m=0 to 1.0, and n=1-m. mula (IV) as noted above, wherein the cross-linking reaction In a further preferred embodiment, the organic polymer is additive is capable of reacting with the cross-linking com a polymer having an aromatic group in the backbone, prefer pound to form a reactive intermediate in the form of an ably a poly(arylene ether), m is 1 and n is 0 and the polymer oligomer for cross-linking an organic polymer, and heating has repeating units along its backbone having the structure of 55 the cross-linking composition Such that oligomerization of formula (V): the cross-linking compound occurs. (V) None embodiment, the method further comprises heating the cross-linking composition before heat molding. In an alternative embodiment, the method further comprises heat 60 ing the cross-linking composition during heat molding. O O O The cross-linking compound used in the method may have any of the various structures as noted above. In one embodi ment, the cross-linking reaction additive is an organic acid and/or acetate as described above. 65 In one embodiment, the method further comprises combin ing the cross-linking compound and the cross-linking reac tion additive in a solvent and reacting the cross-linking com US 9,109,080 B2 7 8 pound and the cross-linking reaction additive to form a In one embodiment, the cross-linking compound has a reactive oligomerized cross-linking compound. In an alterna structure according to formula (IV): tive embodiment, the method further comprises combining the cross-linking compound and the cross-linking reaction additive in solid form. (IV) The method of forming an organic polymer composition may also include the steps of adding the reactive oligomer ized cross-linking compound to an organic polymer to form a cross-linkable composition, cross-linking the organic poly mer composition to form across-linked organic polymer. The 10 organic polymer of the method can one of the various poly mers noted above, including the preferred polyarylene poly mers having a repeating unit as in formula (V). The present invention also includes heat-molded articles useful for down-hole and other extreme condition end appli 15 cations which are formed from the organic polymer compo sitions and methods as described above. The articles may be wherein A is an arene moiety having a molecular weight of formed by various methods or techniques including extru less than 10,000 g/mol, R' is selected from a group consisting Sion, injection molding, blow molding, blown film molding, of hydroxide (-OH), amine ( NH), halide, ether, ester, or compression molding and/or injection/compression molding. amide, and X is about 2.0 to about 6.0. Preferably, the articles include, for example, but are not lim In further embodiments, the cross-linking compound has a ited to acid-resistant coatings, chemical-casted films, structure selected from a group consisting of extruded films, solvent-casted films, blown films, encapsu lated products, insulation, packaging, composite cells, con nectors, and sealing assemblies in the shape of O-rings, 25 V-rings, U-cups, gaskets, bearings, valve seats, adapters, wiper rings, chevron back-up rings, and tubing. In addition to use of the compounds noted above, the appli cants herein have observed that as viscosity increases in Such aromatic group-containing organic polymers, the degree of 30 inhibition which can be achieved from using such cross linking reaction additives for rate control may not always be Sufficient Such that in Some embodiments herein, additional modification is desirable to improve end effects be reducing and/or controlling the curing and cross-linking rate. 35 Thus, Applicant has also developed a solution to the need in the art for easier, Smooth processing and heat molding of cross-linked organic polymers, either formed using tech niques described herein or formed using prior art techniques, allowing for use of traditional molding techniques which 40 require a window of curing which can be longer than what may be achieved using a direct cross-linking process as in the prior art techniques noted above and/or even over and above the inhibition effects achieved using Applicant's enhanced cross-linking reaction additives as described above and else 45 where herein. Thus, the invention further provides debrominated organic polymers for cross-linking, particularly useful for those organic polymers having an aromatic group in the backbone and/or that are in the category of high glass transition tem 50 perature polymers, as well as compositions including Such dehalogenated organic polymers and methods for preparing and cross-linking the same. The resulting articles are formed using controlled cross-linking reaction rates enabling use of traditional molding techniques during crosslinking of Such 55 polymers due to the enhanced (processability of the dehalo genated organic polymers. The invention opens an avenue for creating a variety of unique and readily moldable cross-linked organic polymer articles of manufacture providing the ben eficial properties of such materials, including chemical resis 60 tance, high-temperature and high-pressure performance and strength for a variety of end applications. Included herein is an organic polymer composition for use in forming a cross-linked aromatic polymer, comprising a dehalogenated organic polymer and at least one cross-linking 65 compound. In one embodiment, the dehalogenated organic polymer is a debrominated organic polymer. US 9,109,080 B2 10 selected from Sulfate, phosphate, hydroxyl, carbonyl, ester, -continued halide, mercapto or potassium. The acetate compound is preferably selected from lithium acetate hydrate, Sodium acetate, and/or potassium acetate, and salts and derivatives thereof. The weight percentage ratio of the cross-linking compound to the cross-linking reaction additive may preferably be about 10:1 to about 10,000:1, and more preferably about 20:1 to about 1,000:1. 10 The weight percentage ratio of the dehalogenated organic polymer to a combined weight of the cross-linking compound and the cross-linking reaction additive may be, for example, about 1:1 to about 100:1, and preferably about 3:1 to about 10:1. 15 The dehalogentated organic polymer is (preferably a poly mer selected from poly(arylene ether)s, polysulfones, poly etherSulfones, polyimides, polyamides, polyureas, polyure thanes, polyphthalamides, polyamide-imides, poly (benzimidazole)s and polyaramids. The dehalogenated organic polymer may also be a polymer in one embodiment herein that is a poly(arylene ether) includ ing polymer repeating units along its backbone having the following structure:

25 wherein Ar", Ari, Ar and Arare identical or different aryl radicals, m=0 to 1.0, and n=1-m. In a further preferred embodiment, the dehalogenated organic polymer is a polymer having an aromatic group in the 30 backbone, preferably a poly(arylene ether), m is 1 and n is 0 and the polymer has repeating units along its backbone hav ing the structure of formula (V):

35

The arene moiety may have a molecular weight of about 1,000 g/mol to about 9,000 g/mol, or more preferably about 40 2,000 g/mol to about 7,000 g/mol. The composition may also further comprise a cross-linking reaction additive selected from an organic acid and/or an go acetate compound, wherein the cross-linking reaction addi tive is capable of reacting with the cross-linking compound to 45 forma reactive intermediate in the form of an oligomer, which At least one additive may also be provided to the compo reactive intermediate oligomer is capable of cross-linking the sition, and the additive(s) may be continuous or discontinu dehalogenated organic polymer. ous, long or short, reinforcing fibers selected from carbon Such a cross-linking reaction additive may be an organic fibers, glass fibers, woven glass fibers, woven carbon fibers, 50 aramid fibers, boron fibers, polytetrafluorethylene fibers, acid selected from glacial acetic acid, formic acid, and/or ceramic fibers, polyamide fibers; and one or more fillers benzoic acid. The cross-linking reaction additive in a further selected from carbon black, silicate, fiberglass, calcium Sul embodiment is an acetate compound having a structure fate, boron, ceramic, polyamide, asbestos, fluorographite, according to formula (II): aluminum hydroxide, barium sulfate, calcium carbonate, 55 magnesium carbonate, silica, alumina, aluminum nitride, borax (sodium borate), activated carbon, pearlite, Zinc tereph (II) O thalate, graphite, talc, mica, silicon carbide whiskers or plate lets, nanofillers, molybdenum disulfide, fluoropolymer, car bon nanotubes and fullerene tubes. M-O ls CHR2 60 In one embodiment, the additive(s) comprise reinforcing fibers selected from a group consisting of continuous or dis wherein M is a Group I or a Group II metal; and R is a alkyl, continuous, long or short, carbon fibers, polytetrafluoroeth aryl or aralkyl group, wherein the alkyl group comprises a ylene fibers, and glass fibers. If such additives are used as hydrocarbon group of 1 to about 30 carbon atoms which has noted above, the composition preferably has about 0.5% to from 0 to about 10 ester or ether groups, preferably 0 to about 65 about 65% by weight of the at least one additive, and more 5 such groups, along or in a chain or structure of the group, preferably about 5.0% to about 40% weight of the at least one and wherein R* comprises 0 to about 10 functional groups additive. US 9,109,080 B2 11 12 In addition, the composition may further comprise a stabi lizer, a flame retardant, a pigment, a plasticizer, a Surfactant, and or a dispersant. The dehalogenated organic polymer is preferably formed, in one embodiment herein, by reacting an organic polymer 5 having at least one halogen-containing reactive group with an alkali metal compound to break the bond between the organic O COO polymer having the at least one halogen-containing reactive group and the halogen atom in the at least one halogen containing reactive group to form an intermediate having a 10 On O carbocation. The intermediate having the carbocation is reacted with acetic acid to form the debrominated organic polymer. In one embodiment, the halogen-containing reac The at least one halogen-containing reactive group is pref erably represented by R (X), wherein R is carbon or a tive group is a bromine-containing reactive group. 15 The alkali metal compound useful in Such a dehalogena branched or straight chain organic group selected from alkyl, tion reaction is preferably one haying the structure R M', alkenyl, aryland aralkyl groups of from 1 to about 30 carbon wherein M' is an alkali metal and R is H or a branched or atoms having from 0 to about 10 ester or ether groups along or straight chain organic group selected from alkyl, alkenyl, aryl in a chain or structure of the group, preferably from 0 to about and aralkyl groups of from 1 to about 30 carbonatoms having 5 of such groups, and wherein R* may be substituted or from 0 to about 10 ester or ether groups along or in a chain or unsubstituted; and wherein X is a halogen atom and p is an structure of the group, and wherein R may be substituted or integer that is 1 or 2. unsubstituted. In one embodiment herein, the alkali metal compound is The alkali metal compound may in one preferred embodi selected from the group consisting of R. M', wherein M' is ment herein be t-butyllithium. The organic polymer having at 25 an alkali metal and R is H or a branched or straight chain least one halogen-containing end group. Such as a bromine organic group selected from alkyl, alkenyl, aryl and aralkyl containing reactive group, is preferably reacted with the groups of from 1 to about 30 carbon atoms having from 0 to alkali metal compound in a solvent, and the organic polymer about 10 ester or ether groups, preferably 0 to about 5 such having at least one halogen-containing end group is also groups, along or in a chain or structure of the group, and preferably dried prior to reacting in the solvent. 30 wherein R may be substituted or unsubstituted, and may be The invention also includes molded articles formed from t-butyllithium. the compositions noted above and described further herein. The organic polymer having the at least one halogen-con The invention also includes a method of controlling the taining end group is preferably reacted with the alkali metal cross-linking reaction rate of an organic polymer having at compound in a solvent according to an embodiment of the least one halogen-containing reactive group during a cross 35 method described herein. The solvent is preferably one which linking reaction, preferably organic polymers having an aro is capable of dissolving the organic polymer having the at matic group in the backbone chain of the polymer. The least one halogen-containing reactive group and is free of method comprises: (a) reacting the organic polymer having at functional groups that react with the halogen in the halogen least one halogen-containing reactive group with an alkali 40 containing reacting group under reaction conditions in step metal compound to break the bond between the organic poly (a) noted above. Suitable solvents include a heptane, a hex merhaving the at least one halogen-containing reactive group ane, tetrahydrofuran, and a diphenyl ether. The organic polymer having the at least one halogen-con and the halogen atom in the at least one halogen-containing taining end group is also preferably dried prior to reacting reactive group and thereby forming an intermediate having a with the alkali metal compound in the solvent. carbocation; (b) reacting the intermediate having the carboca 45 The first reaction step of a dehalogenation treatment pref tion with acetic acid to form a dehalogenated organic poly erably occurs at a temperature of less than about -20°C., and mer, and (c) crosslinking the dehalogenated organic polymer more preferably about -70° C. for a period of about 2 hours. using a crosslinking reaction. Step (c) of the method noted above, may further comprise: The at least one halogen-containing reactive group is gen reacting the dehalogenated organic polymer with a cross erally a terminal group and the organic polymer may be any of 50 linking compound. Such a cross-linking compound has the those noted above, such as poly(arylene ether)s, polysul structure according to formula (IV): fones, polyetherSulfones, polyimides, polyamides, poly ureas, polyurethanes, polyphthalamides, polyamide-imides, poly(benzimidazole)s and polyaramids, and is preferably one (IV) having an aromatic group in the backbone chain of the poly 55 mer. In one embodiment, the organic polymer having the halogen-containing reactive group is poly(arylene ether) including polymer repeating units along its backbone having the following structure: 60 wherein Ar", Ar., Ar and Art are identical or different aryl radicals, m=0 to 1.0, and n=l-m. In one embodiment, such an organic polymer is a poly(arylene ether), m is 1 and n is 0 and 65 the polymer has repeating units along its backbone having the wherein A is an arene moiety having a molecular weight of structure of formula (V): less than 10,000 g/mol, R' is selected from a group consisting US 9,109,080 B2 13 14 of hydroxide (—OH), amine ( NH), halide, ether, ester, or FIG. 1 is a graphical representation of the thermal rate of amide, and X is about 2.0 to about 6.0. cure of an organic polymer composition after combination Step (c) may also further comprise providing a cross-link with a product of a cross-linking composition comprising a ing reaction additive selected from an organic acid and/or an cross-linking compound and an organic acid; acetate compound, wherein the cross-linking reaction addi- 5 FIG. 2 is a is a graphical representation of the thermal rate tive is capable of reacting with the cross-linking compound to of cure of an organic polymer composition after combination forma reactive intermediate in the form of an oligomer, which with a cross-linking compound and an organic acid; reactive intermediate oligomer is capable of cross-linking the FIG. 2A is graphical representation of the cure times versus dehalogenated organic polymer. the oligomerization reaction times in 5000FP Blends of The cross-linking reaction additive may be an organic acid 10 organic polymer compositions; selected from glacial acetic acid, formic acid, and/or benzoic FIG.3 is a is a graphical representation of the thermal rate acid. The cross-linking reaction additive may also be an of cure of an organic polymer composition after combination acetate compound having a structure according to formula with a cross-linking compound and an acetate compound; (II): 15 FIG. 3A is a graphical representation of the controlled thermal rate of cure that correlates with the percent of oligo merized cross-linking compound that has been added to an (II) organic polymer composition; O FIG. 4A is a photographic representation of an injection ls 2O molded articles of manufacture of a molded organic polymer M-O CHR2 composition containing a non-oligomerized cross-linking compound; wherein M is a Group I or a Group II metal; and R is a alkyl, FIG. 4B is a photographic representation of injection aryl or aralkyl group, wherein the alkyl group comprises a molded articles of manufacture of a molded organic polymer hydrocarbon group of 1 to about 30 carbon atoms which has 25 composition containing with an oligomerized cross-linking from 0 to about 10 ester or ether groups, preferably 0 to about compound; 5 such groups, along or in a chain or structure of the group, FIG. 5 is a graphical representation described in Example and wherein R* comprises 0 to about 10 functional groups 6 as Graph A. selected from Sulfate, phosphate, hydroxyl, carbonyl, ester, FIG. 6 is a graphical representation described in Example halide, mercapto or potassium. 30 6 as Graph B; and The acetate compound is preferably selected from lithium FIG. 7 is a prior art graph from Parallel Plate Rheology of acetate hydrate, sodium acetate, and/or potassium acetate, Blend 3, at 380° C., referenced to J. Mercel et al., “Thermal and salts and derivatives thereof. Analysis of Polymers: Fundamentals and Applications.” p. Step (c) noted above may also include heating the cross 445, Wiley, ed. 1 (2009). linking compound and the cross-linking reaction additive in a 35 separate composition Such that oligomerization of the cross DETAILED DESCRIPTION OF THE INVENTION linking compound occurs to form the reactive intermediate oligomer. The method may also comprise adding the reactive Described herein are cross-linking compositions that intermediate oligomer to the dehalogenated organic polymer include a cross-linking compound and one or more reactive to form a cross-linkable composition and then cross-linking 40 cross-linking additives, as well as organic polymer composi the cross-linkable composition to form a cross-linked organic tions for use informing a cross-linked organic polymer, meth polymer. ods for preparing Such compositions and polymers, and The method may also further comprise heat molding the articles of manufacture formed from the aforementioned cross-linked organic polymerto form a heat-molded article of compositions and by Such methods which are useful extreme manufacture. The article of manufacture may be formed by 45 condition end applications such as in down-hole applications. heat molding using techniques such as extrusion, injection In the present invention, cross-linking compositions con molding, blow molding, blown film molding, compression taining a cross-linking compound(s) and a cross-linking reac molding or injection/compression molding. tion additive(s) can be reacted to form a reactive oligomerized The articles of manufacture made herein may be acid cross-linking intermediate either in situ during thermal mold resistant coatings; chemical-casted films; extruded films; Sol- 50 ing with a cross-linkable organic polymer, and/or by reacting Vent-casted films; blown films; encapsulated products; insu prior to combining with a cross-linkable organic polymer and lation; packaging; composite cells; connectors; sealing then heat molding to form an article. This intermediate oli assemblies, including O-rings, V-rings, U-cups, gaskets; gomer reaction product of the cross-linking compound with bearings; valve seats; adapters; wiper rings; chevron back-up the crosslinking reaction additive enables control of a cross rings; and tubing. 55 linking reaction when combined with an organic polymer and can enable a lower rate of thermal cure, to allow a broader BRIEF DESCRIPTION OF THE SEVERAL window and better control during heat mold of the resultant VIEWS OF THE DRAWINGS cross-linked organic polymer. Also described herein is a cross-linked organic polymer The foregoing Summary, as well as the following detailed 60 composition capable of providing an inhibited and/or con description of preferred embodiments of the invention, will trolled cross-linking reaction rate and a method for molding be better understood when read in conjunction with the articles from cross-linked organic polymers using Such com appended drawings. For the purpose of illustrating the inven position. The compositions and methods herein enable easier tion, there is shown in the drawings embodiments which are use of traditional (or non-traditional) heat molding tech presently preferred. It should be understood, however, that the 65 niques to form articles from cross-linked organic compounds invention is not limited to the precise arrangements and without worrying about the window of process formation instrumentalities shown. In the drawings: being inconsistent with the rate of cure, so that premature US 9,109,080 B2 15 16 crosslinking curing is reduced or eliminated during part for mation resulting in uniform parts formed from more easy-to process compositions. In general, formation of cross-links in an organic polymer cross-linking to itself or in an organic polymer composition 5 comprising an unmodified cross-linking compound may be completed within about 2 minutes at about 380°C., the typi cal processing temperature of polyetherether ketone (PEEK). The extent of this reaction can be tracked by dynamic viscos ity measurements. Two methods are often used to judge when a reaction may be completed. The point where storage modu 10 lus G equals Loss modulus G", called the crossover point or gel point, indicates the onset of gel formation where cross linking has produced an interconnected. As curing continues, G' will increase, which is an indication of cross-link density. As curing continues, eventually G will level off, which indi- 15 cates that most curing is completed. The inflection point G'. which indicates onset of vitrification can also be used in cases where no obvious cross-over point can be determined (See FIG. 7). The time required to attain G'; G" crossover or the onset of vitrification can be used as the upper limit of process 20 time for a thermosetting material. Utilization of one or more cross-linking reaction addi tive(s) in the invention helps to provide polymers with high glass transition temperatures and high cross-link density. Polymers with high thermal stability of up to 500° C., and as high crosslink density, while desirable, display a very high melt viscosity before further processing, and thus are very difficult to melt process. As curing of the cross-linked poly mer may be initiated during heat molding, it is desirable to control when cross-linking begins. If the rate of cross-linking is not controlled before molding of a composition into a final 30 article, the article of manufacture may begin to prematurely cure before or during heat molding or proceed too rapidly causing incomplete mold fill, equipment damage, and inferior properties in the article. Thus, the invention improves control of the rate of cross-link formation in an organic polymer. The 35 addition of the cross-linking reaction additive as described herein to the cross-linking compound used for cross-linking organic polymers can delay the onset of cross-linking in the organic polymer for as much as several minutes to allow for rapid processing and shaping of the resultant organic polymer 40 structures in a controlled manner. One or more cross-linking compounds is/are present in the cross-linking composition and organic polymer compositions herein. Preferably, the cross-linking compound has a struc ture according to Formula (IV): 45

(IV)

55

wherein A is an arene moiety having a molecular weight of 60 less than 10,000 g/mol. R' can be hydroxide (-OH), amine ( NH), halide, ether, ester, or amide, and X is about 2.0 to about 6.0. The arene moiety A on the cross-linking compound above provides the cross-link site for forming more complex cross- 65 linking compound structures, including, for example, without limitation: US 9,109,080 B2 17 18 -continued The arene moiety A may also be functionalized, if desired, using one or more functional groups such as, for example, and without limitation, Sulfate, phosphate, hydroxyl, carbonyl, ester, halide, or mercapto. The cross-linking compound can be formed, for example, by treating a halogenated arene with an alkyllithium in order to exchange the halogen with lithium, followed by the addi tion of 9-florenone and acid. This method of formation is described and shown in more detail in International Patent 10 Application Publication No. WO 2013/074120 A1, which is incorporated herein by reference in relevant part concerning the method of formation. The cross-linking composition and the organic polymer composition also contain a cross-linking reaction additive. The cross-linking reaction additive(s) include organic acids and/or acetate compounds, which can promote oligomeriza tion of the cross-linking compound. In one embodiment, the The arene moiety A may be varied to have different structures, oligomerization cat be carried out by acid catalysis using one including, but not limited to the following: or more organic acid(s), including glacial acetic acid, acetic acid, formic acid, lactic acid, citric acid, oxalic acid, uric acid, benzoic acid and similar compounds. An oligomerization reaction using one of the cross-linking compounds listed above is as follows: 25

HOAc -e- 30 cyclohexanone reflux

35

40

45

In other embodiments, inorganic acetate compounds, such as those having a structure according to formula (II) below may also be used instead of or in combination with the 50 organic acids:

(II) O 55 M-O ls CHR2 wherein Misa Group I or a Group II metal. R in Formula (II) The arene moiety A is most preferably the diradical of 60 may preferably be an alkyl, aryl or aralkyl group. For 4,4'-biphenyl, or example, R may be a hydrocarbon group of 1 to about 30 carbonatoms, preferably 1 to about 15 carbon atoms, includ ing normal chain and isomeric forms of methyl, ethyl, propyl. pentyl, hexyl, heptyl, octyl, nonyl, decyl ethenyl, propenyl, 65 butenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, and the -() ()- like. R* may also have from 0 to about 10 ester or ether groups along or in a chain of the hydrocarbon group, and preferabyl US 9,109,080 B2 19 20 about 0 to about 5 such ester or ether groups. Suitable Raryl -continued and aralkyl groups, including those based on phenyl, naph O thyl, and similar groups, which may each include optional lower alkyl groups on the aryl structure of from 0 to about 10 4. carbonatoms, preferably about 0 to about 5 carbon atoms. R may further include 0 to about 10, preferably 0 to about 5, functional groups if desired Such as Sulfate, phosphate, hydroxyl, carbonyl, ester, halide, mercapto and/or potassium on the structure. A 10 ) GE ( Oligomerization of the cross-linking compound with an acetate compound can afford the same resultant oligomerized cross-linking composition as achieved when adding an ( ) OH ( ) organic acid. The cross-linking reaction additive may be A-arene

lithium acetate hydrate, Sodium acetate, potassium acetate, 15 acetate, cesium acetate, francium acetate, beryllium acetate, , , strontium acetate, , and/or radium acetate, and salts and derivatives thereof. More preferably, the cross-linking reac tion additive is acetate hydrate, sodium acetate and/or potas sium acetate, and salts and derivatives of such compounds. An oligomerization reaction using of one of the cross-linking compounds can proceed as follows:

25 O O -k's N le. -:)H - H1 NH 30 ketene ( ) HO ( ) 35 ( ) OH ( ) 40

A-arene and higher oligomers 45 The cross-linking composition preferably has a weight percentage ratio of the cross-linking compound to the cross H3C O linking reaction additive of about 10:1 to about 10,000:1, and 50 more preferably about 20:1 to about 1000:1 for achieving the best results. In making the cross-linking composition, in one embodiment, the components are combined prior to addition of an organic polymer to make an organic polymer composi K) OH ( ) tion. Alternatively, they may all be combined simultaneously. 55 The amount of the cross-linking compound in the cross A-arene linking composition is preferably about 70% by weight to about 98% by weight, more preferably about 80% by weight to about 98% by weight, and most preferably about 85% by HC O weight to about 98% by weight based on the weight of the 60 cross-linking composition. The amount of the cross-linking reaction additive in the cross-linking composition is prefer ably about 2% by weight to about 30% by weight, more preferably about 2% by weight to about 20% by weight, and ()" ( ) most preferably about 2% by weight to about 15% by weight. 65 The organic polymer composition for use in forming a A-arene cross-linked polymer includes at least one organic polymer. The at least one organic polymer may be one of a number of US 9,109,080 B2 21 22 higher glass transition temperature organic polymers, such 95% by weight, and most preferably about 75% by weight to as, but not limited to poly(arylene ether)s, polysulfones, poly about 90% by weight based on the total weight of an unfilled etherSulfones, polyimides, polyamides, polyureas, polyure organic polymer composition including the cross-linking thanes, polyphthalamides, polyamide-imides, poly(benzimi compound, the cross-linking reaction additive and the dazole)s and polyaramids. Preferably the polymers are non organic polymer. functionalized, in that they are chemically inert and they do The organic polymer composition may further be filled not bearany functional groups that are detrimental to their use and/or reinforced and include one or more additives to in down-hole tool articles of manufacture or end applications. improve the modulus, impact strength, dimensional stability, More preferably, the organic polymer is a poly(arylene heat resistance and electrical properties of composites and ether) including polymer repeating units of the following 10 other finished articles of manufacture formed using the poly Structure: mer composition. These additive(s) can be any Suitable or useful additives known in the art or to be developed, including without limitation continuous or discontinuous, long or short, wherein Ar", Ar., Ar and Ar may be the same or different reinforcing fibers such as, for example, carbon fiber, glass aryl radicals, such as those groups listed above as the arene 15 fiber, woven glass fiber, woven carbon fiber, aramid fiber, moieties for the cross-linking compound, m=0 to 1.0, and boron fiber, PTFE fiber, ceramic fiber, polyamide fiber and n=1-m. the like; and/or one or more fillers such as, for example, More preferably, the organic polymer is a poly(arylene carbon black, silicate, fiberglass, calcium Sulfate, boron, ether) having a structure according to the general structure ceramic, polyamide, asbestos, fluorographite, aluminum above wherein n is 0 and m is 1, with repeating units accord hydroxide, barium Sulfate, calcium carbonate, magnesium ing formula (V) and having a number average molecular carbonate, silica, alumina, aluminum nitride, borax (sodium weight (Mn) of about 10,000 to about 30,000: borate), activated carbon, pearlite, Zinc terephthalate, graph ite, talc, mica, silicon carbide whiskers or platelets, nanofill ers, molybdenum disulfide, fluoropolymer fillers, carbon 25 nanotubes and fullerene tubes. Preferably, the additive(s) include reinforcing fiber Such as continuous or discontinuous, long or short, carbon fiber, PTFE fiber, and/or glass fiber. In making the organic polymer composition, it is preferred that the additive(s) is/are added to the composition along with 30 or at about the same time that the oligomerized cross-linking composition (or the combined components thereof) is com bined with the organic polymer to make an organic polymer composition, however, the manner of providing reinforcing fibers or other fillers may be according to various techniques 35 for incorporating such materials and should not be considered Such organic polymers may be obtained commercially for to limit the scope of the invention. The amount of additives is example, as UlturaTM from Greene, Tweed and Co., Inc., preferably about 0.5% by weight to about 65% by weight Kulpsville, Pa. based on the weight of the organic polymer composition, and The organic polymer composition preferably has a weight more preferably about 5.0% by weight to about 40% by percentage ratio of the organic polymer to the combined 40 weight. weight of the cross-linking compound and the cross-linking In addition, the organic polymer composition may further reaction additive of about 1:1 to about 100:1, and more pref comprise other compounding ingredients, including stabiliz erably about 3:1 to about 10:1 for achieving the best results. ers, flame retardants, pigments, plasticizers, Surfactants, and/ In making the organic polymer composition, it is preferred or dispersants such as those known or to be developed in the that the cross-linking compound and the cross-linking reac 45 art to aid in the manufacturing process. In making the organic tion additive components are combined prior to addition of an polymer composition, it is preferred that the one or more organic polymer to make an organic polymer composition. fillers is/are added to the organic polymer composition along Alternatively, they may all be combined simultaneously. with or at about the same time that the oligomerized The amount of the cross-linking compound in the organic crosslinking composition (or the combined components polymer composition is preferably about 1% by weight to 50 thereof) is combined with the organic polymer to make an about 50% by weight, more preferably about 5% by weight to organic polymer composition, however, as noted above, the about 30% by weight, and most preferably about 8% by manner of providing such materials may be according to weight to about 24% by weight based on the total weight of an various techniques and should not be considered to limit the unfilled organic composition including the cross-linking Scope of the invention. The amount of the compounding compound, the cross-linking reaction additive and the 55 ingredients that can be combined into the organic polymer organic polymer. composition, if used, is preferably about 5% by weight to The amount of the cross-linking reaction additive in the about 60% by weight of a total of such ingredients based on organic polymer composition is preferably about 0.01% by the weight of the organic polymer composition, more prefer weight to about 33% by weight, more preferably about 0.1% ably about 10% by weight to about 40% by weight, and most by weight to about 10% by weight, and most preferably about 60 preferably about 30% by weight to about 40% by weight. 0.2% by weight to about 2% by weight based on the total In an embodiment of the method of the invention, after weight of an unfilled organic polymer composition including providing, for example by manufacturing, a cross-linking the cross-linking compound, the cross-linking reaction addi composition as described herein, the cross-linking composi tive and the organic polymer. tion is heated to induce oligomerization of the cross-linking The amount of the organic polymer in the organic polymer 65 compound as shown in Examples 1 and 4. In one embodiment composition is preferably about 50% by weight to about 99% of the method, the oligomerization occurs by acid catalysis. by weight, more preferably about 70% by weight to about Acid catalysis is used when an organic acid is employed as the US 9,109,080 B2 23 24 cross-linking additive. The R' functionality of the cross-link ite cells, connectors, and sealing assemblies in the shape of ing compound of Formula (IV) is dissociated from the O-rings, V-rings, U-cups, gaskets, bearings, valve seats, remainder of the compound to afford a carbocation which adapters, wiper rings, chevron back-up rings, and tubing. then can undergo a Friedel-Crafts alkylation the organic poly The above embodiments of invention will now be mer, resulting in bond formation. In another embodiment of described in accordance with the following, non-limiting the method of the present invention, oligomerization of the examples: cross-linking compound may occur by doping. Doping is accomplished by physically mixing solid form reactants in EXAMPLE 1. the composition at lower temperatures of about -100° C. to Preparation of a Cross-Linking Composition Using an about -300° C. prior to reacting the overall composition for 10 Organic Acid Cross-Linking Additive. A 15.34g portion of curing and/or heat molding the resulting composition to form the cross-linking compound identified as Diol-2 in Examples an article. 2 and 4 of International Patent Application Publication No. The method may further comprise adding the reacted oli WO 2013/074120A1 was dissolved in a mixture of 20 mL of gomerized cross-linking composition to an organic polymer glacial acetic acid and 300 mL of cyclohexanone. The solu to form a cross-linkable composition as demonstrated in 15 tion was heated to reflux for a total of 13.5 hours, after which Examples 2 and 5. The unmodified cross-linking compound the glacial acetic acid and cyclohexanone were removed via may be added directly to the organic polymer and blended atmospheric distillation. The product was a pasty Solid resi with the cross-linking reaction additive to simultaneously due, 1H and 13C NUR data indicates a 1:00:1:00 molar ratio oligomerize and bind to the organic polymeras demonstrated ofC OH to the cardo carbon of the cross-linking compound. in Example 3. Once the reactive oligomerized cross-linking compound reacts with the organic polymer, the rate of cross EXAMPLE 2 linking of the organic polymer occurs at a later time in the curing process as compared to the rate of cross-linking that Preparation of an Organic Polymer Composition after Oli would occur in an organic polymer composition having a gomerization of the Cross-Linking Compound Using an prior art cross-linking composition using the same crosslink 25 Organic Acid Cross-Linking Additive. A 0.85g portion of the residue of Example 1 was combined with 9.15g of 5000FP ing compound but without the cross-linking reaction additive. Polyether ether ketone (PEEK) powder. Analysis was con The result is complete filling of the mold and a more excellent ducted by an AR2000 Rheometer with 8 mm parallel plates end heat molded/extruded, etc. product formed from the com and an inert nitrogen purge to determine the rate of cure. posite polymer during various heat molding techniques (See Samples were loaded and stabilized for 4.5 minutes at 380° FIGS. 4A and 4B which show the difference in a finished part 30 C., and 60-minute time sweep tests were performed to record formed without and with, respectively, a crosslinking reactive the change in the modulus to determine the rate of cure for 50 additive). minutes. The results are shown in FIG. 1. Powders of the organic polymer compositions of the present invention were made into pellets, and the pellets were EXAMPLE 3 Subjected to a heat molding process. Heat molding of the 35 organic polymer compositions can be accomplished by many Preparation of an Organic Polymer Composition During different means already known or to be developed in the art, Oligomerization of the Cross-Linking Compound Using an including extrusion, injection molding, compression molding Organic Acid Cross-Linking Additive. 13.725 g of 5000FB and/or injection/compression molding. As shown in FIG. 4B, Polyether ether ketone (PEEK) powder was combined with pellets of an organic polymer composition of the present 40 1.275 g of the above-noted cross-linking compound Diol-2, invention were injection molded on an Arbug.R. 38-ton injec 100 mL cyclohexanone, and 20 mL. glacial acetic acid in a 500 tion molding machine with a cold runner system that includes ml RBF equipped with a magnetic stir bar. After 4 hours a hot sprue. Bars made with a prior art unmodified cross reflux time, the glacial acetic acid and cyclohexanone were linking compound as shown in FIG. 4A were not able to be removed using a short path still, followed by drying in a completely filled, even with 36,000 psi fill pressure. However, 45 vacuum oven at 120 for 20 hours. Analysis was conducted by bars made with the reactive oligomerized cross-linking inter an AR2000 Rheometer with 8 mm parallel plates and an inert mediate compounds of the present invention were able to be nitrogen purge to determine the rate of cure. Samples were processed and completely filled with only 26,000 psi fill loaded and stabilized for 4.5 minutes at 380° C., and pressure. 60-minute time sweep tests were performed to record the Heat molding to form an article of manufacture may be 50 change in the modulus to determine the rate of cure for 50 accomplished by any method known or to be developed in the minutes. The results are summarized in Table 1 and shown in art including but not limited to heat cure, cure by application FIGS. 2 and 2A. of high energy, heat cure, press cure, steam cure, a pressure cure, an e-beam cure or cure by any combination of means, TABLE 1 etc. Post-cure treatments as are known in the art or to be 55 developed may also be applied, if desired. The organic poly Reaction Cross Over Inflection mercompositions of the present invention are cured by expos COSS- time, (G' = G"), Point, ing the composition to temperatures greater than about 250 Sample % linker hrs SeC. SeC. C. to about 500° C., and more preferably about 350° C. to Control 8% O.OO O 128 about 450° C. 60 Example 3 8% 4.OO O 298 The compositions and/or the methods described above Example 2 8% 13.50 3500 3500 may be used in or to prepare articles of manufacture of down hole tools and applications used in the petrochemical indus try. Particularly, the article of manufacture is selected from EXAMPLE 4 the group consisting of acid-resistant coatings, chemical 65 casted films, extruded films, solvent-casted films, blown Preparation of a Cross-Linking Composition Using an films, encapsulated products, insulation, packaging, compos Acetate Compound Cross-Linking Additive. Four blends of US 9,109,080 B2 25 the cross-linking compound Diol-2 identified above and TABLE 3 lithium acetate dehydrate were prepared using a Spex.R. 6870 % Cross Over Inflection freezer mill. Samples were cooled in liquid nitrogen at COSS- % (G' = G"), Point, approximately -195° C. for 15 min., then ground for 12 Sample linker Additive SeC. SeC. cycles for 3 min., followed by 5 minutes of cooling for a total Control 8% OOOOO% O 128 of 96 min. grinding time at -196°C. at a speed of 10 cycles/s. Blend 1 8% O.225.0% 256 1036 Blend 2 8% O4SOO% 1317 1836 No solvents were used in this Example. The weight amounts Blend 3 8% O9000% 1665 2203 of each component of the composition is listed in Table 2 Blend 4 8% 3.OOOO% 88 818 below: 10 The Applicant has also discovered that part of the lack of TABLE 2 control and fast cure of compositions of crosslinkable organic polymers, particularly those having aromatic groups in the Mass of backbone chain, and including those having rate-controlling lithium % lithium acetate 15 additives as noted above, is the presence of reactive end acetate Mass of dihydrate in groups, particularly those having halogen-containing reactive Blendii dehydrate Diol-2 Diol-2 groups, such as bromine-containing reactive end groups. An example of a cross-linked polyarylene ether polymer having 1 0.225 g 9.775 g O.225 a halogen-containing reactive end group, in this instance, a 2 0.45 g 9.55 g O.45 bromine-containing end group which is a bi-phenyl bromide group is shown below in formula (III):

(III) UO CS CO O O Br

40 TABLE 2-continued Such end groups can negatively impact processing and prop erties of cross-linked organic polymers. The treatment of such Mass of lithium % lithium acetate polymers, which are typically formed using a compound for acetate Mass of dihydrate in cross-linking, to remove of such end groups results in a mate Blendii dehydrate Diol-2 Diol-2 45 rial that is significantly more processable than the same poly mer without Such treatment. 3 0.90 g 9.10 g O.90 4 0.317 g 0.8 g. 28.4 Typical synthesis procedures yield number average molecular weights (Mn) of about 20,000 to about 25,000 daltons, and a repeat unit of a polymer Such as that shown in 50 formula III would have about 502 daltons. Thus, there would EXAMPLE 5 be about 46 repeat units in a polymer of a number average molecular weight of 24,000 in a given batch. Each polymer Preparation of an Organic Polymer Composition after Oli chain has at least two end groups. As the polymer is a con gomerization of the Cross-Linking Compound Using an 55 densation polymer, there is roughly a 50% chance of a halo Acetate Compound Cross-Linking Additive. An 8.0 g portion gen-containing end group, such as the bromine-containing of the oligomerized cross-linker composition of Blend 2 in group, biphenyl bromine end group as shown in formula III Example 4 was combined with 92 g of 5000FP Polyether above, being present. Thus, each Such polymer is expected to ether ketone (PEEK) powder in a 500 mL bottle and was have about one of the bromine-containing end groups per shaken at 45 rpm for 30 minutes. Analysis was conducted by 60 chain, corresponding to an approximate bromine level of an AR2000 Rheometer with 8 mm parallel plates and an inert about 3,100 to 4,000 ppm for polymers having a single bro nitrogen purge to determine the rate of cure. Samples were mine end group. If the polymer incorporates two Such end loaded and stabilized for 4.5 minutes at 380° C., and groups, the bromine level could be as much as 6,200 to about 60-minute time sweep tests were performed to record the 8,000 ppm bromine. The applicants did a bromine analysis of change in the modulus to determine the rate of cure for 50 65 a typical polymer in this category having a number average minutes. The results are summarized in Table 3 and in FIGS. molecular weight of 25.300 which yielded a bromine level of 3 and 3A. 3,400 ppm, which was within theoretical predictions. US 9,109,080 B2 27 28 The biphenyl bromine end group and other similar end groups is/are not expected to be as thermally stable as the (B) aromatic cross-linked backbone and thus may be thermally cleaved during processing at high temperatures (of about 350° C. to about 400° C.). For example, the phenyl-bromine 5 ( ) OH HO ( ) ( ) HO ( ) bond is known in the art to be weak, and the bromine radical very reactive. Thus, heating of brominated aromatics at high temperatures can result in the phenyl-bromine bond breaking to produce a bromine radical and a phenyl radical. See, 10 Ladacki et al., Proceedings of the Royal Society of London: Series A. Mathematical and Physical Sciences, (1953) 219, 11, pp. 341-352, “Studies of the Variations in Bond Dissocia tion Energies of Aromatic Compounds, I. Monobromo 15 4-(X- aryles. The bromine radical, as with other halogens, being Aromatic Polymer extremely reactive, will rapidly abstract a proton to produce HX (wherein X is a halogen) as a byproduct. With respect to bromine, HBr forms and is an acid which is known to react with hydroxyl groups of 3 trityl alcohols to form carboca 2O tions via an acid-base reaction and to form tritylbromide, which is the conjugate acid of the trityl alcohol, and water. OH S. The Applicant herein observed that the hydroxyl groups of 9.9'-(biphenyl-4,4'-diyl)bis(9H-fluoren-9-ol) behave very 25 similarly to trityl alcohol in this regard. Thus, the resulting HBr acts as an initiator and will then generate a reactive carbocation which thus accelerates cross-linking (see reac ~ X tion scheme shown in (A) below). This behavior can partly 30 Aromatic Polymer counteract the degree of control provided by the reactive cross-linking additives described above that inhibit reaction rate, and further, may speed up cross-linking. 35 / Aromatic Polymer

40

HO A O) - - 45 Aromatic Polymer ( )

50 Lithium acetate and similar compounds as described here inabove act as basic inhibitors to moderate the thermal acti O vation of the phenylfluorenol end groups and to inhibit for mation of a reactive carbocation. However, in Such a reaction scheme, acidic HBr or other similar halogen acids generated 55 through thermal decomposition of the cross-linked polymer end groups, for example, can react with the basic acetate anion to neutralize it, thus at the same time neutralizing the inhibiting effect of the reactive additive. Continuing this evaluation using the lithium acetate as the A thermally produced carbocation generated by the loss of 60 prospective reactive additive for controlling reaction rate of the hydroxyl group of 9.9'-(biphenyl-4,4'-diyl)bis(9H-fluo the cross-linking reaction, the theoretical molar quantity of HBr or other similar acid that may be generated is approxi ren-9-ol) becomes a reactive intermediate and likely a rate mately 2.4 times higher than the molar quantity of lithium limiting step in initiation of a cross-linking reaction. A pro acetate dihydrate (base) added as the inhibiting reaction addi posed reaction mechanism (B) for the cross-linking reaction 65 tive. Thus, the instinctual path to overcome this issue would of an organic polymer using 9.9'-(biphenyl-4,4-diyl)bi(9H be to incorporate high concentrations of lithium acetate or fluoren-9-ol) and related variants is shown below. other reactive additives with inhibiting effect to neutralize the US 9,109,080 B2 29 30 acid being generated. Unfortunately, when too much excess with an organic polymer generally, particularly those with and/or higher amounts of Such inhibiting reactive additives, aromatic groups in the backbone, but can enable even lower e.g., lithium acetate, are used, it can contribute to a contrary rates of thermal cure and allow a broader window and better effect in the presence of the halogen acid as the excess addi control and reaction rate inhibition during heat mold when a tive may actually begin to accelerate the reaction, thus limit dehalogenated organic polymer is used as a base polymer. ing the range of effectiveness of the additives noted in the As noted above, formation of cross-links in an organic invention described above in a complex reaction mechanism. polymer cross-linking to itselfor in an organic polymer com In addition to issues impacting reaction rate aside from position comprising an unmodified cross-linking compound generation of a halogen acid, Such as HBr, the product of a may be completed within about 2 minutes at about 380° C. thermal dehydrohalogenation reaction during cross-linking 10 the typical processing temperature of polyetherether ketone may create a very reactive aryl radical or benzyne intermedi (PEEK) (FIG. 7). ate. The reactive aryl intermediate generated by thermally Utilization of one or more cross-linking reaction addi tive(s) has been identified to help provide polymers with high induced dehydrohalogenation could itself act as a thermally glass transition temperatures and high cross-link density cure activated cross-link site and is difficult to control due to the more stably when combined with a cross-linking compound exothermic nature of reactions such as those between 9.9'- 15 such as that of formula (IV). Polymers with high thermal (biphenyl-4,4'-diyl)bis(9H-fluoren-9-ol) and a crosslinking stability of up to 500° C. and high crosslink density, while organic polymer Such as a polyarylene ether, which exother desirable, as mentioned above, display a very high melt vis mic reaction profile can be observed and evaluated via Dif cosity before further processing, and thus are very difficult to ferential Scanning calorimetry (DSC). The exothermic melt process. If the rate of cross-linking is not controlled curves can be used to estimate half-lives of exothermic reac before molding of a composition into a final article, the article tions via the Borchardt and Daniels Method. See, ASTM of manufacture may begin to prematurely cure before or E2041, Standard Test Method for Estimating Kinetic Param during heat molding or proceed too rapidly causing incom eters by Differential Scanning Calorimeter Using the plete mold fill, equipment damage, and inferior properties in Borchardt and Daniels Method. This method allows calcula the article. Thus, the invention is also directed to improving tion of activation energies and other kinetic parameters. Once 25 by controlling or inhibiting the rate of cross-link formation in these rate coefficients are obtained, reaction half lives at vari an organic polymer using the cross-linking compound(s) and/ ous temperatures can be calculated. The half lives obtained or the cross-linking reaction additive(s) as described above in for various treatments of polymers and inhibitors can then be combination with a dehalogenated organic polymer, Such as a compared to estimate the improvement in cure time (cross debrominated organic polymer, which is capable of cross linking reaction time) gained by specific treatments. 30 linking. This provides a reaction wherein the inhibitor(s) (not With the foregoing information in mind, the Applicant impeded by X or HX formation, such as B or HBr) can work herein discovered that contrary to the above problematic more effectively and delay the onset of cross-linking in the approaches, it is possible to chemically remove the halogen organic polymer for as much as several minutes beyond what is achieved without the dehalogenation treatment of the initial from a halogen-containing end group but to control the halo polymer to allow for rapid processing and shaping of the gen-containing byproducts and enable formation of purified 35 resultant organic polymer structures in a controlled manner. organic polymers, in the sense that Such polymers are deha In the organic polymer compositions herein for use in logenated prior to cross-linking. Such dehalogenated, puri forming a cross-linked organic polymer, the composition fied organic polymers are then capable of being easily cross includes at least one organic polymer that is dehalogenated. linked and molded, so that there is a slower and more Polymers which can benefit in a preferred manner by a deha compatible, controlled cross-linking reaction during mold 40 logenation treatment prior to crosslinking in include at least ing, and traditional heat-molding techniques may be readily one organic polymer that may be one of a number of higher used. glass transition temperature organic polymers and/or which Cross-linked articles formed from cross-linking the deha have an aromatic group in the backbone of the polymer, logenated organic polymers using a cross-linking compound including, but not limited to, for example, poly(arylene ether) and optionally one or more reactive cross-linking additives 45 S. polysulfones, polyetherSulfones, polyimides, polyamides, according to the invention described herein, as well as organic polyureas, polyurethanes, polyphthalamides, polyamide polymer compositions having a dehalogenated organic poly imides, poly(benzimidazole)s and polyaramids. Preferably merand a cross-linking compound for use informing a cross the polymers are non-functionalized, in that they are chemi linked organic polymer. In addition, methods for preparing cally inert and they do not bear any functional groups that are Such compositions and polymers, and articles of manufacture 50 detrimental to their use in down-hole tool articles of manu facture or end applications. Such polymers if able to benefit formed from the aforementioned compositions and by Such from a dehalogenation treatment prior to cross-linking would methods are within the invention and are useful in extreme also have at least one halogen-containing reactive group. condition end applications such as in down-hole applications. Generally Such groups, as discussed above, are generally Cross-linking compositions containing a cross-linking terminal groups which may remain from the polymerization compound(s) can be reacted to form a reactive oligomerized 55 process or other end-capping reactions and the like. cross-linking intermediate either in situ during thermal mold More preferably, in one embodiment herein, the organic ing in combination with a cross-linkable dehalogenated polymer is a poly(arylene ether) Such as those noted above organic polymer, and/or by reacting a separate cross-linking including polymer repeating units in the backbone of the composition having a cross-linking compound(s) and a cross polymer chain having the following structure: linking reaction additive(s) to form the oligomerized cross 60 linking intermediate and then combining the oligomerized cross-linking intermediate with a cross-linkable dehaloge wherein Ar", Ari, Ar and Ar" may be the same or different nated organic polymer and heating and molding the com aryl radicals, such as those groups listed above as the arene bined materials to forman article. The intermediate oligomer moieties for the cross-linking compound, m=0 to 1.0, and reaction product of the cross-linking compound(s) with the 65 n=1-m. optional crosslinking reaction additive(s)act as inhibitors and More preferably, the organic polymer is a poly(arylene enable control of a cross-linking reaction when combined ether) having a structure according to the general structure US 9,109,080 B2 31 32 above wherein n is 0 and m is 1, with repeating units accord chain or structure of the group, and wherein R* may be sub ing formula (V) and having a number average molecular stituted or unsubstituted. Suitable alkyls include methyl, weight (Mn) of about 10,000 to about 30,000: ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl, pentyl, hepty1 and the like. Suitable alkenyls include methenyl, ethe nyl, propenyl, iso-propenyl, butenyl, iso-butenyl, tert-bute nyl, pentenyl, and the like. Aryl groups may be single or multiple ring structures, such as benzyl, phenyl, Xylyl, biphe nyl, dibenzyl, and the like, and Such groups may be modified to have aryl or aralkyl groups or side chains and to form 10 aralkyl structures as well. X represents a halogen, bromine, iodine, chlorine, flourine, and the like, and p is an integer O COO which is 1 or 2. The reaction of the organic polymer having the halogen containing reactive group preferably occurs with an alkali On O 15 metal compound. The alkali metal compound may be repre sented by R M', wherein M' is an alkali metal and R may be H or a branched or straight chain organic group selected As noted above. Such organic polymers may be obtained from alkyl, alkenyl, arylandaralkyl groups of from 1 to about commercially for example, as UlturaTM from Greene, Tweed 30 carbon atoms, preferably about 1 to about 15 carbon and Co., Inc., Kulpsville, Pa. atoms, having from 0 to about 10 ester or ether groups, pref Other Suitable organic polymers for use in the invention as erably 0 to about 5 such groups, along or in a chain or struc noted above, Such as polyarylenes and polyarylene ethers, ture of the group. R may be a substituted or unsubstituted may be made with, for example, diiodobiphenyl monomer group. The Substituted groups may include functional groups and/or dibromobiphenyl monomers. In Such instances, the for providing other properties to the resulting polymer, pro method used herein should be used to remove the bromine 25 vided they do not affect the dehalogenated organic polymer containing or iodine-containing reactive groups to deiodinate ultimately formed from the process and/or do not impact the or debrominate the polymer. For other suitable polymers, reaction or rate thereof of the organic polymer having the Such as polysulfones, many are formed using chlorinated halogen-containing reactive halogen group or negatively monomers in synthesis which may leave chlorine-containing impact the reaction between such polymer with the alkali reactive groups, and the method herein should be used to 30 metal. Such functional groups may include, for example, dechlorinate the chlorine-containing reactive groups. Thus, it hydroxyl, carbonyl, ester, halide, mercapto and/or potassium. should be understood to one skilled in the art, that for organic Suitable alkali metal compounds include methyl lithium, polymers having halogen-containing reactive groups that are methenyl lithium, ethyl lithium, ethenyl lithium, isoproypl present from formation by a polymerization process leaving lithium, propyl lithium, propenyl lithium, butyl lithium, reactive, halogen-containing groups, such as halogen-con 35 isobutyl lithium, t-butyl lithium, s-butyl lithium, n-butyl taining end groups, such organic polymers can be dehaloge lithium, butenyl lithium, and similar compounds, methyl nated to provide purified organic polymers for use in cross Sodium, methenyl Sodium, ethyl sodium, ethenyl Sodium, linking reactions where rate control is an issue in employing isopropyl Sodium, propyl Sodium, propenyl sodium, n-butyl Such polymers in traditional heat molding processes. Sodium, S-butyl sodium, t-butyl sodium, butenyl sodium, and To dehalogenate the organic polymer, an organic poly 40 similar compounds, methyl potassium, methenyl potassium, mer(s) alone or in combination may be subjected to the ethyl potassium, ethenyl potassium, propenyl potassium, method of the present invention. The method provides a deha butyl potassium, isobutyl potassium, n-butyl potassium, S-bu logenated organic polymer which works in the cross-linking tyl potassium, t-butyl potassium, butenyl potassium, and composition to control the cross-linking reaction rate of an similar compounds, as well as, for example, benzyl lithium, organic polymer having at least one halogen-containing reac 45 phenyl lithium, benzyl Sodium, phenyl Sodium, benzyl potas tive group during a cross-linking reaction. In the method, an sium, phenyl potassium, and other related compound. Pref organic polymer having a halogen-containing reactive group. erably, the alkali metal compound is butyl lithium, t-butyl Such as those noted above, and preferably having one or two lithium, butyl sodium, t-butyl sodium, butyl potassium or halogen-containing terminal groups, such as bromine, iodine, t-butyl potassium. chlorine and the like, is used. 50 The organic polymer having the at least one halogen-con The polymer having the halogen-containing reactive group taining end group is reacted with the alkali metal compound is reacted with an alkali metal compound to break the bond preferably in a solvent environment. The solvent is preferably that connected the halogen atom to the polymer, that is, the capable of dissolving the organic polymer having the at least bond between the organic polymer having the at least one one halogen-containing reactive group but free of functional halogen-containing reactive group and the halogen atom in 55 groups that react with the halogen in the halogen-containing the at least one halogen-containing reactive group. This reac reactive group under the reaction conditions used. Suitable tion forms an intermediate having a carbocation. Solvents include, but are not limited to heptane, hexane, tet The at least one halogen-containing reactive group is typi rahydrofuran, and diphenyl ether as well as similar solvents cally a halogen atom (X) but more often the halogen atom and derivatives or functionalized variants of Such solvents, links to the chain, and most typically in a terminal position, by 60 with the most preferred solvent being tetrahydrofuran (THF). a final organic group off of the primary backbone. Such a The reaction preferably occurs at low temperatures of less reactive group may be represented as —R (X). wherein than about -20°C., preferably less than about -50° C., and R" is carbon or a branched or straight chain organic group more preferably less than about -70° C. so as to minimize selected from alkyl, alkenyl, aryland aralkyl groups of from potential side reaction between the solvent used and the alkali 1 to about 30 carbon atoms, preferably 1 to about 20 carbon 65 metal compound. For example, as the half life of t-butyl atoms, having from 0 to about 10 ester or ether groups, pref lithium THF at -20°C. is about 42 minutes, by reacting it erably 0 to about 5 such ether or ester groups along or in a below that temperature, for example, at -70° C. to -78°C., US 9,109,080 B2 33 34 further time is provided, as the estimated half life of that -continued compound in THF is about 1300 minutes. Thus the reaction H3C No.1 CH proceeds as desired and reactive interference by thermal -- L-Br issues is minimized. The reaction preferably proceeds until a CH3 majority of halogen atoms are removed from the organic 5 Li" polymer, preferably Substantially all of the halogen atoms, N. O and most preferably virtually all or all of the halogen atoms -- are removed. Reaction times will vary depending on the Sol 2 HO ul CH3 —- vent used, the alkali metal compound and the temperature of H O the reaction, hut is expected to continue for about 0.5 to about 10 4 hours, and preferably about 1 to about 2 hours. O CH3. Before introducing the organic polymer to Such a solvent R O Li" ul reaction, it is preferred that the organic polymer having the at least one halogen-containing reactive group to be reacted in 15 solvent with the alkali metal compound is first dried as a While the above mechanism shows a preferred method for preparatory step before reacting the polymer with the alkali dehalogenation herein, other reactions and methods for metal compound in the solvent. Such a drying step may be removing halogen from Such organic polymers may also be conducted in any suitable manner for the purpose of minimiz used within the scope of the invention. See, for example, J. ing or removing adsorbed water from the polymer, as water Moon et al., “Hydrogenolysis of Aryl Halides by Hydrogen may interfere with the reaction. One acceptable non-limiting Gas and Hydrogen Transfer over Palladium-Supported Cata method for drying the polymers is to oven-dry them in a lysts. Vol. 3, issue 6, Comptes Rendus L'Académie des Sci vacuum oven at a temperature Suitable for the polymer cho ences—Chemistry, pp. 465-470 (November 2000). Dehalo sen. For a polyarylene polymer, temperatures of about 100° genation may also be carried out via treatments with Grignard 25 reagents. Grignard Degradation, Comprehensive Organic C. to about 200° C., more preferably about 110° C. to about Name Reactions and Reagents, pp. 1271-1272 (September 120° C. are suitable. Oven drying should occur until the 2010). polymer is at least Substantially dry, and for approximately at After dehalogenation of the organic polymer, the dehalo least 10 hours, preferably at least 15 hours, and most prefer genated organic polymer can be introduced into a cross ably about hours, with the understanding that drying times 30 linking reaction and will provide enhanced performance to may also vary depending on the polymer and the level of Such reaction. Any Suitable graft, reaction, or similar cross adsorbed water in the pre-treated polymer. Drying can be linking reaction may be used. Preferably cross-linking occurs Verified via various types of moisture analysis, for example, using a cross-linking compound as described above. Karl Fischer coulometric titration of the polymer dissolved in Thus, an organic polymer composition may be formed THF, measuring the dew point on an air dryer, or by loss of 35 weight via thermogravimetric analysis (TGA) at tempera including the dehalogenated organic polymer and a cross tures less than about 250'C. linking compound. Any Suitable cross-linking compound that would create a cross-linked organic polymer from the deha Once the dried organic polymer having the halogen-con logenated organic polymer may be used. As an example of taining reactive group(s) is dissolved in the solvent and one such system, a dehalogenated organic polymer having an reacted with the alkali metal compound, an intermediate 40 forms having a carbocation. This intermediate and the con aromatic group in the backbone, may be cross-linked using a tinuing reaction is then quenched by reacting the intermediate cross-linking compound that is preferred is one having a having the carbocation with acetic acid or a similar acetate structure noted above according to formula (IV): group containing acid to form a dehalogenated organic poly 45 C. (IV) One reaction scheme for this reaction using a polyarylene polymer wherein the halogen-containing reactive group is diphenyl bromine, is shown below in reaction scheme C, wherein R represents the polymer chain of formula (III) above including the first phenyl group in the terminal, diphe nyl bromine group. ) A

(C) ()" B 55 r H3C CH3 -- -e- wherein A is an arene moiety having a molecular weight of R Li CH less than 10,000 g/mol, R' is selected from a group consisting -- of hydroxide (—OH), amine ( NH), halide, ether, ester, or No. Li H3C CH3 60 amide, and X is about 2.0 to about 6.0. One or more cross-linking compounds is/are present in the R 21 Br XCH3 cross-linking composition and may be combined with the dehalogenated organic polymers in Such compositions. H3C CH3 H3C CH3 CH The arene moiety A on the cross-linking compound above X X -- HC-( 65 provides the cross-link site for forming more complex cross Br CH3 Li CH3 CH linking compound structures, including, for example, without limitation: US 9,109,080 B2 35 36 -continued

The arene moiety A may be varied to have different structures, including, but not limited to the following: * - St.3 T

30 K / KK)-( y1) 35 Ks / \ X 45 ng& K ) { 2y

50

55

60

65 In addition, the arene moiety A is most preferably the diradical of 4,4'-biphenyl, or US 9,109,080 B2 37 38 potassium acetate, and salts and derivatives of Such com pounds. An oligomerization reaction using of one of the cross-linking compounds is shown above. -() ()- The cross-linking composition preferably has a weight percentage ratio of the cross-linking compound to the cross The arene moiety A may also be functionalized, if desired, linking reaction additive of about 10:1 to about 10,000:1, and using one or more functional groups such as, for example, and more preferably about 20:1 to about 1000:1 for achieving the without limitation, Sulfate, phosphate, hydroxyl, carbonyl, best results. In making the cross-linking composition, in one embodiment, the components are combined prior to addition ester, halide, or mercapto. The cross-linking compound can 10 be formed as noted above. of a dehalogenated organic polymer to make an organic poly The cross-linking composition and the organic polymer mer composition according to the invention. Alternatively, composition also contain one or more cross-linking reaction they may all be combined simultaneously. additive(s) as rate-controlling compounds, that is, inhibitors. The amount of the cross-linking compound in the cross The cross-linking reaction additive(s) are preferably the linking composition is preferably about 70% by weight to organic acids and/or an acetate compounds noted above and 15 about 98% by weight, more preferably about 80% by weight should be capable of reacting with the cross-linking com to about 98% by weight, and most preferably about 85% by pound(s) to form a reactive intermediate(s) in oligomeric weight to about 98% by weight based on the weight of the form. Such reactive intermediate oligomer(s) should be cross-linking composition. The amount of the cross-linking capable of cross-linking the dehalogenated organic polymer reaction additive in the cross-linking composition is prefer to have a desired effect. ably about 2% by weight to about 30% by weight, more The cross-linking reaction additive(s) include organic preferably about 2% by weight to about 20% by weight, and acids and/or acetate compounds, which can promote oligo most preferably about 2% by weight to about 15% by weight. merization of the cross-linking compound. In one embodi The organic polymer composition preferably has a weight ment, the oligomerization can be carried out by acid catalysis 25 percentage ratio of the dehalogenated organic polymer to the using one or more organic acid(s), including glacial acetic combined weight of the cross-linking compound and the acid, acetic acid, formic acid, lactic acid, citric acid, oxalic cross-linking reaction additive of about 1:1 to about 100:1, acid, uric acid, benzoic acid and similar compounds. An and more preferably about 3:1 to about 10:1 for achieving the oligomerization reaction using one of the cross-linking com best results. pounds is shown above. 30 In making the organic polymer composition, it is preferred In other embodiments, inorganic acetate compounds, such that the cross-linking compound and the cross-linking reac as those having a structure according to formula (II) may also tion additive components are combined prior to addition of a be used instead of or in combination with the organic acids: dehalogenated organic polymer to make an organic polymer composition. Alternatively, they may all be combined simul 35 taneously. (II) O The amount of the cross-linking compound in the organic polymer composition is preferably about 1% by weight to ls about 50% by weight, more preferably about 5% by weight to M-O CHR2 about 30% by weight, and most preferably about 8% by 40 weight to about 24% by weight based on the total weight of an wherein Misa Group I or a Group II metal. R in Formula (II) unfilled organic composition including the cross-linking may preferably be an alkyl, aryl or aralkyl group. For compound, the cross-linking reaction additive and the deha example, R may be a hydrocarbon group of 1 to about 30 logenated organic polymer. carbon atoms, preferably about 1 to about 15 carbon atoms, The amount of the cross-linking reaction additive in the including normal chain and isomeric forms of methyl, ethyl, 45 organic polymer composition is preferably about 0.01% by propyl, butyl, pentyl, heptyl, octyl, nonyl, decyl ethenyl, weight to about 33% by weight, more preferably about 0.1% propenyl, butenyl, hexenyl, heptenyl, octenyl, nonenyl, dece by weight to about 10% by weight, and most preferably about nyl, and the like. R* may also have from 0 to about 10 ester or 0.2% by weight to about 2% by weight based on the total ether groups, and more preferably about 0 to about 5 such weight of an unfilled organic polymer composition including groups, along or in a chain of the hydrocarbon group. Suitable 50 the cross-linking compound, the cross-linking reaction addi Raryland aralkyl groups, including those based on phenyl, tive and the dehalogenated organic polymer. naphthyl, and similar groups, which may each include The amount of dehalogenated organic polymer in the optional lower alkyl groups on the aryl structure of from 0 to organic polymer composition is preferably about 50% by about 5 carbon atoms. R may further include 0 to about 5 weight to about 99% by weight, more preferably about 70% functional groups if desired Such as Sulfate, phosphate, 55 by weight to about 95% by weight, and most preferably about hydroxyl, carbonyl, ester, halide, mercapto and/or potassium 75% by weight to about 90% by weight based on the total on the structure. weight of an unfilled organic polymer composition including Oligomerization of the cross-linking compound with an the cross-linking compound, the cross-linking reaction addi acetate compound can afford the same resultant oligomerized tive and the dehalogenated organic polymer. cross-linking composition as achieved when adding an 60 The organic polymer composition may further be filled organic acid. The cross-linking reaction additive may be and/or reinforced and include one or more additives to lithium acetate hydrate, Sodium acetate, potassium acetate, improve the modulus, impact strength, dimensional stability, rubidium acetate, cesium acetate, francium acetate, beryllium heat resistance and electrical properties of composites and acetate, magnesium acetate, calcium acetate, strontium other finished articles of manufacture formed using the poly acetate, barium acetate, and/or radium acetate, and salts and 65 mer composition. These additive(s) can be any Suitable or derivatives thereof. More preferably, the cross-linking reac useful additives known in the art or to be developed, as tion additive is lithium acetate hydrate, sodium acetate and/or described above herein. US 9,109,080 B2 39 40 In making the organic polymer composition, it is preferred noted above or other prior art cross-linking systems. The that the additive(s) is/are added to the composition along with result is the ability to more easily use traditional molding or at about the same time that the oligomerized cross-linking techniques and a controlled longer cross-linking time to form composition (or the combined components thereof) is com completely filled molds and excellent manufactured heat bined with the dehalogenated organic polymer to make an 5 molded products. organic polymer composition, however, the manner of pro Powders of the organic polymer compositions of the viding reinforcing fibers or other fillers may be according to present invention can be made into pellets, and the pellets various techniques for incorporating Such materials and Subjected to a heat molding process. Heat molding of the should not be considered to limit the scope of the invention. organic polymer compositions can be accomplished by many The amount of additives is preferably about 0.5% by weight 10 different means already known or to be developed in the art, to about 65% by weight based on the weight of the organic including extrusion, injection molding, compression molding polymer composition, and more preferably about 5.0% by and/or injection/compression molding. Pellets of an organic weight to about 40% by weight. polymer composition of the present invention may be injec In addition, the organic polymer composition may further tion molded, for example, on an Arbug.R. 38-ton injection comprise other compounding ingredients, including stabiliz 15 molding machine with a cold runner system that includes a ers, flame retardants, pigments, plasticizers, Surfactants, and/ hot sprue. or dispersants such as those known or to be developed in the Heat molding to form an article of manufacture may be art to aid in the manufacturing process. In making the organic accomplished by any method known or to be developed in the polymer composition, it is preferred that the one or more art including but not limited to heat cure, cure by application fillers is/are added to the organic polymer composition along of high energy, heat cure, press cure, steam cure, a pressure with or at about the same time that the oligomerized cure, an e-beam cure or cure by any combination of means, crosslinking composition (or the combined components etc. Post-cure treatments may also be applied, if desired. The thereof) is combined with the organic polymer to make an organic polymer compositions of the present invention may organic polymer composition, however, as noted above, the be cured by exposing the composition to temperatures greater manner of providing such materials may be according to 25 than about 250° C. to about 500° C., and more preferably various techniques and should not be considered to limit the about 350° C. to about 450° C. Scope of the invention. The amount of the compounding The compositions and/or the methods described above ingredients that can be combined into the organic polymer may be used in or to prepare articles of manufacture of down composition, if used, is preferably about 5% by weight to hole tools and applications used in the petrochemical indus about 60% by weight of a total of such ingredients based on 30 try. Particularly, articles manufacture may be one or more of the weight of the organic polymer composition, more prefer acid-resistant coatings, chemical-casted films, extruded ably about 10% by weight to about 40% by weight, and most films, solvent-casted films, blown films, encapsulated prod preferably about 30% by weight to about 40% by weight. ucts, insulation, packaging, composite cells, connectors, and In an embodiment of the method of cross-linking accord seating assemblies in the shape of O-rings, V-rings, U-cups, ing to the invention, after providing, for example by manu 35 gaskets, bearings, valve seats, adapters, wiper rings, chevron facturing, a cross-linking composition as described herein, back-up rings, and tubing. the cross-linking composition is heated to induce oligomer The invention will now be further described in accordance ization of the cross-linking compound as in Examples 1 to 4 with the following, non-limiting example: and as noted above. In one embodiment of the method, the oligomerization 40 EXAMPLE 6 occurs by acid catalysis. Acid catalysis is used when an organic acid is employed as the cross-linking additive. The R' In the following example, DSC data was collected on a TA functionality of the cross-linking compound of Formula (IV) Instruments Model Q100DSC at a heating rate of 20°C/min. is dissociated from the remainder of the compound to afford A3 L, 3-neck round-bottomed flask was charged with 1800 a carbocation which then can undergo a Friedel–Crafts alky 45 mL of THF from a freshly opened bottle and 150 g of a dried lation of the organic polymer, resulting in bond formation. In polyarylene polymer having a backbone as shown in formula another embodiment of the method of the present invention, III shown above and at least biphenyl bromine end group on oligomerization of the cross-linking compound may occur by average. The flask was fitted with a mechanical stirrer (half doping. Doping is accomplished by physically mixing Solid moon blade), septum port and a Claison head with thermom form reactants in the composition at lower temperatures of 50 eteran a nitrogen inlet. The flask was kept under nitrogen. For about -100° C. to about -300° C. prior to reacting the overall the few minutes during setup and before nitrogenblanketing, composition for curing and/or heat molding the resulting the materials were handled in ambient air. The reactor was composition to form an article. stirred at room temperature until the organic polyarylene The cross-linking method may further comprise adding the polymer was dissolved which took about 1 hour. The reactor reacted oligomerized cross-linking composition to a debro 55 was cooled to less than -70° C. using a dry ice/acetone bath. minated organic polymer to form a cross-linkable composi With the reactor stirring at 500 to 800 rpm, t-butyllithium tion. The unmodified cross-linking compound may be added was added via cannula at a rate which maintained the reactor directly to the dehalogenated organic polymer and blended temperature below -65° C. This took about 15 min. As the with the cross-linking reaction additive to simultaneously polymer was lithiated, the solution became more viscous. oligomerize and bind to the dehalogenated organic polymer. 60 After 2 hours at less than 70°C., glacial acetic acid was added Once the reactive oligomerized cross-linking compound to neutralize the lithiated polymer. The cooling bath was reacts with the dehalogenated organic polymer, the rate of removed and the reactor was allowed to warm with no bath. cross-linking of the dehalogenated organic polymer occurs at When the temperature was above 0° C., the reaction was a later time in the curing process as compared to the rate of stirred at 100 to 200 rpm while continuing to warm to room cross-linking that would occur in that organic polymer com 65 temperature. After stirring for about 16 hours, the reaction position without dehalogenation treatment and using the mixture was filtered to remove an gel. The polymer was same cross-linking system having the inhibitor additives as precipitated by pouring the filtrate into rapidly stirred metha US 9,109,080 B2 41 42 nol. The debrominated polymer was separated via vacuum acid and/or an acetate compound, wherein the cross-linking filtration and dried under vacuum at 240° C. to remove any compound has a structure according to formula (IV): adsorbed methanol. AGPC analysis showed that the polymer molecular weight remained stable after debromination treatment with no major 5 increases due to crosslinking or decreases due to chain scis (IV) sion. See Table 4 below (wherein Mw is weight average molecular weight) and the molecular weight distribution plot below showing a comparison of the starting organic polymer and the debrominated polymer. 10

TABLE 4 Sample Mn Mw PDI Starting Organic 22,6009 3,200 4.1 15 Polymer Debrominated 23,3009 6,300 4.1 wherein A is an arene moiety having a molecular weight of Organic Polymer less than 10,000 g/mol, R' is selected from the group consist ing of hydroxide (-OH), amine ( NH), halide, ether, ester, The debrominated and starting polymers of the Example or amide, and X is about 2.0 to about 6.0, were crosslinked using a cross-linking compound having a structure as shown below as (D) lithium acetate as a cross wherein the cross-linking reaction additive is capable of linking reaction additive. reacting with the cross-linking compound to form a reactive intermediate in the form of an oligomer, which 25 reactive intermediate oligomer is capable of cross-link

ing an organic polymer. 2. The composition according to claim 1, wherein the cross-linking compound has a structure selected from the group consisting of 30

35 Using the Borchard-Daniels method noted above, the plots below in Graph A of FIG. 5 and Graph B of FIG. 6 show the improvement in half life achieved with the debromination treatment Lithium acetate yielded a half-life change of less 40 than 1 minute to 3 minutes at a temperature of 380°C. The use of the same formulation with a debrominated polymer yielded a half life of approximately 30 minutes. In Graph A. the upper curve represents the debrominated polymer cross linked with 20% of the cross-linking compound noted above 45 and lithium acetate as a cross-linking reactive additive as an inhibitor. The middle curve represents the starting polymer (without debromination treatment) cross-linked with the same amount of cross-linking compounds noted above and using the lithium acetate inhibitor. The lower curve represents the untreated original polymer (without debromination treat ment) cross-linked using the same amount of the cross-link ing compound noted above but without the additional lithium acetate inhibitor. Graph B includes these same three materials exemplified in Graph A, but compares the half life of each at 55 380° C. It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the 60 particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present inven tion as defined by the appended claims.

We claim: 65 1. A composition comprising a cross-linking compound and a cross-linking reaction additive selected from an organic US 9,109,080 B2 43 44

-continued structure of the group, and wherein R* comprises 0 to about 10 functional groups selected from Sulfate, phosphate, hydroxyl, carbonyl, ester, halide, mercapto or potassium. 7. The composition according to claim 6, wherein the acetate compound is selected from lithium acetate hydrate Sodium acetate, and/or potassium acetate, and salts and derivatives thereof. 8. The composition according to claim 1, wherein the weight percentage ratio of the cross-linking compound to the 10 cross-linking reaction additive is about 10:1 to about 10,000: 1. 9. The composition according to claim 8, wherein the weight percentage ratio of the cross-linking compound to the cross-linking reaction additive is about 20:1 to about 1000:1. 15 10. The composition according to claim 1, further compris ing at least one organic polymer, wherein the cross-linking reaction additive is capable of reacting with the cross-linking compound to form a reactive intermediate in the form of an oligomer, which reactive intermediate oligomer is capable of cross-linking the organic polymer. 11. The organic polymer composition according to claim 10, wherein the organic polymer is selected from poly (arylene ether)s, polysulfones, polyetherSulfones, polyim ides, polyamides, polyureas, polyurethanes, polyphthala 25 mides, polyamide-imides, poly(benzimidazole)s and polyaramids. 12. The organic polymer composition according to claim 11, wherein the organic polymer is a poly(arylene ether) including polymer repeating units having the following struc 30 ture:

wherein Ar", Ar., Ar and Art are identical or different aryl radicals, m=0 to 1.0, and n=1-m. 13. The organic polymer composition according to claim 12, wherein the organic polymer is a poly(arylene ether), m is 1 and n is 0 and the polymer has repeating units having the structure of formula (V):

40

45 O CO-O- 3. The composition according to claim 1, wherein the arene moiety has a molecular weight of about 1,000 g/mol to about 9,000 g/mol. OO 4. The composition according to claim3, wherein the arene moiety has a molecular weight of about 2,000 g/mol to about 50 14. The organic polymer composition according to claim 7,000 g/mol. 10, wherein the cross-linking reaction additive is an organic 5. The composition according to claim 1, wherein the acid selected from glacial acetic acid, formic acid and/or cross-linking reaction additive is an organic acid selected benzoic acid. from glacial acetic acid, formic acid, and/or benzoic acid. 15. The organic polymer composition according to claim 6. The composition according to claim 1, wherein the 55 10, wherein the cross-linking reaction additive is an acetate cross-linking reaction additive is an acetate compound having compound having a structure according to formula (II): a structure according to formula (II): (II) (II) O O 60 ls ls M-O CHR2 M-O CHR2 wherein M is a Group I or a Group II metal; and R is a alkyl, wherein M is a Group I or a Group II metal; and R is a alkyl, aryl or aralkyl group, wherein the alkyl group comprises a aryl or aralkyl group, wherein the alkyl group comprises a 65 hydrocarbon group of 1 to about 30 carbon atoms which has hydrocarbon group of 1 to about 30 carbon atoms which has from 0 to about 10 ester or ether groups along or in a chain or from 0 to about 10 ester or ether groups along or in a chain or structure of the group, and wherein R* comprises 0 to about US 9,109,080 B2 45 46 10 functional groups selected from Sulfate, phosphate, wherein A is an arene moiety having a molecular weight of hydroxyl, carbonyl, ester, halide, mercapto or potassium. less than 10,000 g/mol, R' is selected from a group consisting 16. The organic polymer composition according to claim of hydroxide (—OH), amine ( NH), halide, ether, ester, or 10, wherein the weight percentage ratio of the organic poly and amide, and X is about 2.0 to about 6.0, and a cross-linking mer to the combined weight of the cross-linking compound 5 reaction additive selected from an organic acid and/or an and the cross-linking reaction additive is about 1:1 to about acetate compound. 100:1. 25. A molded article formed from the composition of claim 17. The organic polymer composition according to claim 24. 16, wherein the weight percentage ratio of the organic poly 26. A method of controlling the cross-linking reaction rate mer to the combined weight of the cross-linking compound 10 of a cross-linking compound for use in cross-linking an and the cross-linking reaction additive is about 3:1 to about organic polymer, comprising: 10:1. a) providing a cross-linking composition comprising a 18. The organic polymer composition according to claim cross-linking compound and a cross-linking reaction 10, wherein the composition further comprises at least one 15 additive selected from an organic acid and/or an acetate additive selected from continuous or discontinuous, long or compound, wherein the cross-linking compound has the short, reinforcing fibers selected from carbon fibers, glass structure according to formula (IV): fibers, woven glass fibers, woven carbon fibers, aramid fibers, boron fibers, polytetrafluorethylene fibers, ceramic fibers, polyamide fibers; and one or more fillers selected from car (IV) bon black, silicate, fiberglass, calcium sulfate, boron, ceramic, polyamide, asbestos, fluorographite, aluminum hydroxide, barium Sulfate, calcium carbonate, magnesium carbonate, silica, alumina, aluminum nitride, borax (sodium borate), activated carbon, pearlite, Zinc terephthalate, graph 25 ) A ite, talc, mica, silicon carbide whiskers or platelets, nanofill ers, molybdenum disulfide, fluoropolymer, carbon nanotubes and fullerene tubes. () 19. The organic polymer composition according to claim 18, wherein the composition comprises about 0.5% to about 30 65% by weight of the at least one additive. wherein A is an arene moiety having a molecular weight of 20. The organic polymer composition according to claim less than 10,000 g/mol, R' is selected from a group consisting 10, wherein the composition further comprises a stabilizer, a of hydroxide (-OH), amine ( NH), halide, ether, ester, or flame retardant, a pigment, a plasticizer, a Surfactant, and or a amide, and X is about 2.0 to about 6.0, wherein the cross dispersant. 35 linking reaction additive is capable of reacting with the cross 21. A molded article formed from the composition accord linking compound to form a reactive intermediate in the form ing to claim 10. of an oligomer for cross-linking an organic polymer, and 22. The molded article according to claim 21, wherein the b) heating the cross-linking composition Such that oligo article is molded using extrusion, injection molding, blow merization of the cross-linking compound occurs. molding, blown film molding, compression molding or injec 40 27. The method according to claim 26, wherein step (b) tion/compression molding. further comprises heating the cross linking composition 23. An article of manufacture formed from the composition before heat molding. according to claim 10, wherein the article of manufacture is 28. The method according to claim 26, wherein the cross selected from acid-resistant coatings; chemical-casted films; linking reaction additive is an organic acid selected from extruded films; solvent-casted films; blown films; encapsu 45 glacial acetic acid, formic acid and/or benzoic acid, and/oran lated products; insulation; packaging; composite cells; con acetate compound selected from lithium acetate, hydrate nectors; sealing assemblies, including O-rings, V-rings, Sodium acetate, and/or potassium acetate, and salts and U-cups, gaskets; bearings; Valve seats; adapters; wiper rings; derivatives thereof. chevron back-up rings; and tubing. 29. The method according to claim 26, further comprising 24. An organic polymer composition for use in forming a 50 combining the cross-linking compound and the cross-linking cross-linked organic polymer, comprising: reaction additive in Solid form in step (a). an organic polymer; and 30. The method according to claim 26, further comprising a reactive cross-linking oligomer which is a reaction prod combining the cross-linking compound and the cross-linking uct of a cross-linking compound having the structure of reaction additive in a solvent in step (a) and reacting the 55 cross-linking compound and the cross-linking reaction addi formula (IV): tive to form a reactive oligomerized cross-linking compound. (IV) 31. The method according to claim 30, further comprising (c) adding the reactive oligomerized cross-linking com pound to an organic polymer to form a cross-linkable 60 composition and (d) cross-linking the organic polymer composition to form a cross-linked organic polymer. ) A 32. The method according to claim 31, further comprising adding at least one additive in step (c). 65 33. The method according to claim 26, wherein the organic ( )." polymer is selected from poly(arylene ether)s, polysulfones, polyetherSulfones, polyimides, polyamides, polyureas, poly US 9,109,080 B2 47 48 urethanes, polyphthalamides, polyamide-imides, poly(benz (arylene ether), m is 1 and n is 0 and the polymer has repeating imidazole)s and/or polyaramids. units along its backbone having the structure of formula (V): 34. The method according to claim33, wherein the organic polymer is a poly(arylene ether) including polymer repeating units having the following structure: (V) O—Ar. O—Art ), O wherein Ar", Ari, Ar and Arare identical or different aryl radicals, m=0 to 1.0, n=1-m. 35. An organic polymer composition for use in forming a 10 cross-linked organic polymer, comprising: O COO a dehalogenated organic polymer and at least one cross-linking compound; wherein the dehalo genated organic polymer is formed by a process com OO prising reacting an organic polymer having at least one 15 halogen-containing reactive group with an alkali metal compound to breakabond between the organic polymer 42. The organic polymer composition according to claim having the at least one halogen-containing reactive 35, wherein the composition further comprises at least one group and a halogen atom in the at least one halogen additive selected from continuous or discontinuous, long or containing reactive group to form an intermediate. short, reinforcing fibers selected from carbon fibers, glass 36. The organic polymer composition according to claim fibers, woven glass fibers, woven carbon fibers, aramid fibers, 35, wherein the dehalogenated organic polymer is a debro boron fibers, polytetrafluorethylene fibers, ceramic fibers, minated organic polymer. polyamide fibers; and one or more fillers selected from car 37. The organic polymer composition according to claim bon black, silicate, fiberglass, calcium sulfate, boron, 35, wherein the cross-linking compound has a structure 25 ceramic, polyamide, asbestos, fluorographite, aluminum according to formula (IV): hydroxide, barium Sulfate, calcium carbonate, magnesium carbonate, silica, alumina, aluminum nitride, borax (sodium borate), activated carbon, pearlite, Zinc terephthalate, graph (IV) ite, talc, mica, silicon carbide whiskers or platelets, nanofill ers, molybdenum disulfide, fluoropolymer, carbon nanotubes and fullerene tubes. 43. The organic polymer composition according to claim 35, wherein the dehalogenated organic polymer is formed by reacting an organic polymer having at least one halogen containing reactive group with an alkali metal com pound to break a bond between the organic polymer having the at least one halogen-containing reactive group and a halogen atom in the at least one halogen wherein A is an arene moiety having a molecular weight of 40 containing reactive group, and to form an intermediate; less than 10,000 g/mol R' is selected from a group consisting and of hydroxide (—OH), amine ( NH), halide, ether, ester, or reacting the intermediate with acetic acid to form the deha amide, and X is about 2.0 to about 6.0. logenated organic polymer. 38. The organic polymer composition according to claim 44. The organic polymer composition according to claim 35, further comprising a cross-linking reaction additive 45 43, wherein the alkali metal compound is selected from the selected from an organic acid and/or an acetate compound, group consisting ofR M', wherein M' is an alkali metaland wherein the cross-linking reaction additive is capable of R is Hora branched or straight chain organic group selected reacting with the cross-linking compound to form a reactive from alkyl, alkenyl, arylandaralkyl groups of from 1 to about intermediate in the form of an oligomer, which reactive inter 30 carbon atoms having from 0 to about 10 ester or ether mediate oligomer is capable of cross-linking the dehaloge 50 groups along or in a chain or structure of the group, and nated organic polymer. wherein R may be substituted or unsubstituted. 39. The organic polymer composition according to claim 45. The organic polymer composition according to claim 35, wherein the dehalogenated organic polymer is a polymer 44, wherein the alkali metal compound is t-butyllithium. selected from poly(arylene ether)s, polysulfones, polyether 46. The organic polymer composition according to claim Sulfones, polyimides, polyamides, polyureas, polyurethanes, 55 43, wherein the halogen-containing reactive group is a bro polyphthalamides, polyamide-imides, poly(benzimidazole)S mine-containing reactive group. and polyaramids. 47. The organic polymer composition according to claim 40. The organic polymer composition according to claim 43, wherein the organic polymer having at least one halogen 39, wherein the dehalogenated organic polymer is a poly containing end group is reacted with the alkali metal com (arylene ether) including polymer repeating units in its back 60 pound in a solvent and the organic polymer having the at least bone having the following structure: one halogen-containing end group is dried prior to reacting in the solvent. O—Art ), 48. A molded article formed from the composition accord wherein Ar", Ari, Ar and Arare identical or different aryl ing to claim 35. radicals, m=0 to 1.0, and n=1-m. 65 49. A method of controlling the cross-linking reaction rate 41. The organic polymer composition according to claim of an organic polymer having at least one halogen-containing 40, wherein the dehalogenated organic polymer is a poly reactive group during a cross-linking reaction, comprising: US 9,109,080 B2 49 50 a) reacting the organic polymer having at least one halo functional groups that react with the halogen in the halogen gen-containing reactive group with an alkali metal com containing reactive group under reaction conditions for step pound to break a bond between the organic polymer (a). having the at least one halogen-containing reactive 56. The method according to claim 55, wherein the solvent is selected from a heptane, a hexane, tetrahydrofuran, and a group and a halogen atom in the at least one halogen diphenyl ether. containing reactive group, and to form an intermediate 57. The method according to claim 54, wherein the organic having carbocation; polymer having the at least one halogen-containing end group b) reacting the intermediate having the carbocation with is dried prior to reacting with the alkali metal compound in the acetic acid to form a dehalogenated organic polymer; solvent. and 10 58. The method according to claim 49, wherein step (a) c) crosslinking the dehalogenated organic polymer using a occurs at a temperature of less than about -20°C. crosslinking reaction. 59. The method according to claim 58, wherein step (a) 50. The method according to claim 49, wherein the at least occurs at a temperature of less than about -70° C. for a period one halogen-containing reactive group is a terminal group of about 2 hours. 15 60. The method according to claim 49, wherein step (c) and the organic polymer having the at least one halogen further comprises: containing reactive group is a polymer selected from poly reacting the dehalogenated organic polymer with a cross (arylene ether)s, polysulfones, polyetherSulfones, polyim linking compound. ides, polyamides, polyureas, polyurethanes, 61. The method according to claim 60, wherein step (c) polyphthalamides, polyamide-imides, poly(benzimidazole) further comprises providing a cross-linking reaction additive s, and polyaramids. selected from an organic acid and/or an acetate compound, 51. The method according to claim 49, wherein the at least wherein the cross-linking reaction additive is capable of one halogen-containing reactive group is represented by reacting with the cross-linking compound to form a reactive -R (X), wherein R is carbon or a branched or straight intermediate in the form of an oligomer, which reactive inter chain organic group selected from alkyl, alkenyl, aryl and 25 mediate oligomer is capable of cross-linking the dehaloge aralkyl groups of from 1 to about 30 carbon atoms having nated organic polymer. from 0 to about 10 ester or ether groups along or in a chain or 62. The method according to claim 61, further comprising structure of the group, and wherein R* may be substituted or before step (c) heating the cross-linking compound and the unsubstituted; and X is a halogenatom and p is an integer that cross-linking reaction additive in a separate composition Such is 1 or 2. 30 that oligomerization of the cross-linking compound occurs to 52. The method according to claim 49, wherein the alkali form the reactive intermediate oligomer. metal compound is selected from the group consisting of 63. The method according to claim 49, further comprising R. M', wherein M' is an alkali metal and R is H or a heat molding the cross-linked organic polymer to form a branched or straight chain organic group selected from alkyl, heat-molded article of manufacture. alkenyl, aryland aralkyl groups of from 1 to about 30 carbon 35 64. The method according to claim 63, wherein the article atoms having from 0 to about 10 ester or ether groups along or of manufacture is heat molded using extrusion, injection in a chain or structure of the group, and wherein R may be molding, blow molding, blown film molding, compression substituted or unsubstituted. molding or injection/compression molding. 53. The method according to claim 52, wherein the alkali 65. The method according to claim 63, wherein the article metal compound is t-butyllithium. 40 of manufacture is selected from acid-resistant coatings; 54. The method according to claim 49, wherein the organic chemical-casted films; extruded films; solvent-casted films; polymer having the at least one halogen-containing end group blown films; encapsulated products; insulation; packaging; is reacted with the alkali metal compound in a solvent. composite cells; connectors; sealing assemblies, including 55. The method according to claim 54, wherein the solvent O-rings, V-rings, U-cups, gaskets; bearings; Valve seats; is capable of dissolving the organic polymer having the at 45 adapters; wiper rings; chevron back-up rings; and tubing. least one halogen-containing reactive group and is free of k k k k k UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 9,109,080 B2 Page 1 of 1 APPLICATIONNO. : 14/059064 DATED : August 18, 2015 INVENTOR(S) : Kerry A. Drake et al. It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below:

In the Claims Column 44, line 32, the formula “- (O - Ari- O - Ara - )(- O - Ars - O - Ara-), of claim 12 should read as follows: --- (O - Ar- O - Ar—)(- O - Ar—O — Ar—), --

Column 47, line 7, the formula “- (O - Ari- O - Ara - )(- O - Ars - O - Ara-), of claim 34 should read as follows: --- (O - Ar- O - Ar—)(- O - Ar' - O - Ar"—), --

Column 47, line 63, the formula “- (O - Ari- O - Ara - )(- O - Ars - O - Ara-), of claim 40 should read as follows: --- (O-Ar- O - Ar—),(- O - Ar' - O - Ar—), --

Signed and Sealed this Nineteenth Day of April, 2016 74-4-04- 2% 4 Michelle K. Lee Director of the United States Patent and Trademark Office