CA1246297A - Process for preparing poly(aryl ether ketones) - Google Patents
Process for preparing poly(aryl ether ketones)Info
- Publication number
- CA1246297A CA1246297A CA000503032A CA503032A CA1246297A CA 1246297 A CA1246297 A CA 1246297A CA 000503032 A CA000503032 A CA 000503032A CA 503032 A CA503032 A CA 503032A CA 1246297 A CA1246297 A CA 1246297A
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- Prior art keywords
- chloride
- bis
- carbonyl
- diphenyl
- naphthalene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
- C08G61/127—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from carbon dioxide, carbonyl halide, carboxylic acids or their derivatives
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
AN IMPROVED PROCESS FOR PREPARING
POLY(ARYL ETHER KETONES) ABSTRACT OF THE DISCLOSURE
Described herein is an improved process for preparing poly(aryl ether ketones) by reacting nucleophilic coreactants with electrophilic coreactants under Friedel Crafts polymerization conditions, wherein the improvement comprises carrying out the polymerization in a solvent comprising 1,2-dichlorethane.
S P E C I F I C A T I O N
POLY(ARYL ETHER KETONES) ABSTRACT OF THE DISCLOSURE
Described herein is an improved process for preparing poly(aryl ether ketones) by reacting nucleophilic coreactants with electrophilic coreactants under Friedel Crafts polymerization conditions, wherein the improvement comprises carrying out the polymerization in a solvent comprising 1,2-dichlorethane.
S P E C I F I C A T I O N
Description
L~
AN IMPROVED PROCESS F~R PREPARING
~OLY~AR~L ETHER KETONES~
TECHNICAL FIELD
This invention is directed to an improved process for preparing poly(aryl ether ketones) by reacting a nucleophilic coreactant wi~h an electrophilic coreac.tant under Friedel-Crafts polymeriz~tion conditions, wherein the improvement comprises earrying out ~he polymerization in a solvent comprising 1,2-dichloroethane.
BACKGRQUND OE THE INVENTIQN
The preparation Df poly(aryl ether ketones) by Friedel-Crafts polymerization techniques is well known in the sr~. FDr example, U. S. Pstent No.
3,065,205 describes the preparation of aromatic polyketones by Friedel-Crafts polymerization techniques using an organic solvent for the reactlon. The solYents used are nitrobenzene, symmetrical tetrachl~roethane, dichlorobenzene or carbon disulfide. Nitrobenzene is used as a solvent in all of the examples. The reaction mixture is stated as remaining homogeneous throughout the polymerization. However, the process described in U.S. Patent No. 3,065,205 produces polymers of very low molecular weights ~nd inherent viscosities ranging from 0.13 to 0~18, as me~sured in concentrated sulfuric scid.
In describing the difficulty in preparing polyketones such as those described in U. S. Patent No. 3,065,205, U.S. Patent No. 3,7~1,890 states the problem as the relstively ineractable n~ture of the D-14605 ~ ~
initial polymer-catalyst c~mplex upon formation.
The patent states the follnwing in column l, lines 10 to 20:
"Previous attempts to deal with the gener~lly intract~ble state of the reaction product have included polymerizing the monomers in the presence of a soluble solid msterial ~o permit removing the product from the reaction medium and subsequently separating the soluble material by leaching. However, none of these prior techniques has proved entirely sPtisfRctory. ~
In U. S. Patent No. 3,791,890, an improved process is described in which polyketones are prepared in granular form in a two step process. In the first step diphenyl ether and a~ least one of terephthalic ~r isophthalic acid chlorides are reacted in the presence of o-dichloroben2ene, sym-tetrachloroethane, or dichloroeth~ne as a solvent utilizing a Frledel-Cr~fts catalyst, such as aluminum chloricle, at a temperature of from -15C to 0C. All the examples use o-dichlorobenzene as the solvent. The p~!tent states that an ini~ial low reaction temperature is desirable to maintain control over the rate of reaction so that coagulation of the formed polyketone does not occur before dlspersion can be effected. In the next step, the reaction mixture produced is dispersed into a fluid medium maintained at a tempersture of at least 50~C. The fluid medium ls described as ~ny gas or liQuid in which the polyketone formed is substanti211y unreactive at the temperature employed in the process. The dispersion into a heated fluid is stated to segregate the particles of polymer that 6~
are beginning to form in the initial reaction mixture and prevent the ~gglomeratlon of the particles into a gel~tinous mass. A gr~nul~r polyketone is thus recovered. However, in this patent no viscosities for the polyketone are reported.
In U.S. Patent No. 3,668,057 describes the preparation of copolyketones with reduced viscosities of ~bout 0.9 dl/g (as measured in concentrated sulfuric acid &t 25~C) under Freidel-Crafts polymerization conditions with o-dichlorobenzene ~s solvent. However~ polymers with reduced viscosities of about 0.9dl/g are boardline with regard to toughness in same end-use 2pplicstions. Coployketones with high reduced viscosities sre possible using hydrofluoric acid as the solvent and boron trifluoride 8S the catslyst.
However, due to the toxicity of hydrofluoric ~cidlboron trifluoride it is not a system which is conducive to commercialization.
THE INVENTION
In the present invention a one step process to prepare high molecular weight poly(aryl ether ketones) has been discovered. It has been found that the use of 1,2-dichloroethane 8S a solvent in Friedel-Crafts polymerizstion process produces poly(aryl ether ketones) of high moleculsr weight in comparison to processes where solvents such ~s nitrobenzene and o-dichlorobenzene are utilized.
The process of this invention prepares hi8her molecular weight (reduced viscosity) poly (aryl ~ ~6dj2~7 ether ketones) directly without the need of the disperslon step as required in U.S. Patent No.
3,791,8~0.
The poly(aryl ether ketones) prepared by the process of this invention have reduced viscositles ranging from about 0.1 dl/g to ~bout 3.0 dl/g, preferably from about 0.5 dl/g to ~bout 2.0 dl/~., as measured in concentra~ed sulfuric acid at 2SC ~concentration of lg/lOOml).
The poly(aryl ether ke~ones) may be prepared by reacting:
(8) e mixture of subst~ntially equimolar amounts of ~ i) st least one electrophilic aromatic diacyl halide of the formula YOC-Ar-COY
where -Ar- is a divalent aromatic radical such as phenylene, diphenylether-4,4'-diyl, diphenyl-4,4'-d~yl, naphthalene-diyl, and the like, Y is halogen such as chlorine, bromine or iodine wi~h chlorine being prPferred, snd COY is ~n aromatically bound ficyl halide group, which diacyl halide is polymerizable wi~h at least one aromatic compound of (a~ , and (ii) ~t least one sromatic nucleophilic compound of the formula H-Ar'-H
where -Ar'- is 8 divalent ~romatlc radical such as diphenylether-4,4'-dlyl, 2,7-dibenzofuranediyl, diphenyl-4,4'-diyl, diphenylmethane-4,4'-diyl, naphthalene-diyl, phenanthrenediyl, ~nd the like, and H is an ~romatlcally bound hydrogen atom, which compound is ~-~4605 polymerlzable with at least one diacyl halide of (a)(i~, and (b) ~t least one aromatic monoacyl halide of formula H-Ar"-COY
where -Ar"- is R divalent sromatic radlcal such as diphenylether-4,4'-diyl, diphenylmethane -4,4'-diyl, naphthalene-d-iyl, diphenyl-4,4'-diyl,
AN IMPROVED PROCESS F~R PREPARING
~OLY~AR~L ETHER KETONES~
TECHNICAL FIELD
This invention is directed to an improved process for preparing poly(aryl ether ketones) by reacting a nucleophilic coreactant wi~h an electrophilic coreac.tant under Friedel-Crafts polymeriz~tion conditions, wherein the improvement comprises earrying out ~he polymerization in a solvent comprising 1,2-dichloroethane.
BACKGRQUND OE THE INVENTIQN
The preparation Df poly(aryl ether ketones) by Friedel-Crafts polymerization techniques is well known in the sr~. FDr example, U. S. Pstent No.
3,065,205 describes the preparation of aromatic polyketones by Friedel-Crafts polymerization techniques using an organic solvent for the reactlon. The solYents used are nitrobenzene, symmetrical tetrachl~roethane, dichlorobenzene or carbon disulfide. Nitrobenzene is used as a solvent in all of the examples. The reaction mixture is stated as remaining homogeneous throughout the polymerization. However, the process described in U.S. Patent No. 3,065,205 produces polymers of very low molecular weights ~nd inherent viscosities ranging from 0.13 to 0~18, as me~sured in concentrated sulfuric scid.
In describing the difficulty in preparing polyketones such as those described in U. S. Patent No. 3,065,205, U.S. Patent No. 3,7~1,890 states the problem as the relstively ineractable n~ture of the D-14605 ~ ~
initial polymer-catalyst c~mplex upon formation.
The patent states the follnwing in column l, lines 10 to 20:
"Previous attempts to deal with the gener~lly intract~ble state of the reaction product have included polymerizing the monomers in the presence of a soluble solid msterial ~o permit removing the product from the reaction medium and subsequently separating the soluble material by leaching. However, none of these prior techniques has proved entirely sPtisfRctory. ~
In U. S. Patent No. 3,791,890, an improved process is described in which polyketones are prepared in granular form in a two step process. In the first step diphenyl ether and a~ least one of terephthalic ~r isophthalic acid chlorides are reacted in the presence of o-dichloroben2ene, sym-tetrachloroethane, or dichloroeth~ne as a solvent utilizing a Frledel-Cr~fts catalyst, such as aluminum chloricle, at a temperature of from -15C to 0C. All the examples use o-dichlorobenzene as the solvent. The p~!tent states that an ini~ial low reaction temperature is desirable to maintain control over the rate of reaction so that coagulation of the formed polyketone does not occur before dlspersion can be effected. In the next step, the reaction mixture produced is dispersed into a fluid medium maintained at a tempersture of at least 50~C. The fluid medium ls described as ~ny gas or liQuid in which the polyketone formed is substanti211y unreactive at the temperature employed in the process. The dispersion into a heated fluid is stated to segregate the particles of polymer that 6~
are beginning to form in the initial reaction mixture and prevent the ~gglomeratlon of the particles into a gel~tinous mass. A gr~nul~r polyketone is thus recovered. However, in this patent no viscosities for the polyketone are reported.
In U.S. Patent No. 3,668,057 describes the preparation of copolyketones with reduced viscosities of ~bout 0.9 dl/g (as measured in concentrated sulfuric acid &t 25~C) under Freidel-Crafts polymerization conditions with o-dichlorobenzene ~s solvent. However~ polymers with reduced viscosities of about 0.9dl/g are boardline with regard to toughness in same end-use 2pplicstions. Coployketones with high reduced viscosities sre possible using hydrofluoric acid as the solvent and boron trifluoride 8S the catslyst.
However, due to the toxicity of hydrofluoric ~cidlboron trifluoride it is not a system which is conducive to commercialization.
THE INVENTION
In the present invention a one step process to prepare high molecular weight poly(aryl ether ketones) has been discovered. It has been found that the use of 1,2-dichloroethane 8S a solvent in Friedel-Crafts polymerizstion process produces poly(aryl ether ketones) of high moleculsr weight in comparison to processes where solvents such ~s nitrobenzene and o-dichlorobenzene are utilized.
The process of this invention prepares hi8her molecular weight (reduced viscosity) poly (aryl ~ ~6dj2~7 ether ketones) directly without the need of the disperslon step as required in U.S. Patent No.
3,791,8~0.
The poly(aryl ether ketones) prepared by the process of this invention have reduced viscositles ranging from about 0.1 dl/g to ~bout 3.0 dl/g, preferably from about 0.5 dl/g to ~bout 2.0 dl/~., as measured in concentra~ed sulfuric acid at 2SC ~concentration of lg/lOOml).
The poly(aryl ether ke~ones) may be prepared by reacting:
(8) e mixture of subst~ntially equimolar amounts of ~ i) st least one electrophilic aromatic diacyl halide of the formula YOC-Ar-COY
where -Ar- is a divalent aromatic radical such as phenylene, diphenylether-4,4'-diyl, diphenyl-4,4'-d~yl, naphthalene-diyl, and the like, Y is halogen such as chlorine, bromine or iodine wi~h chlorine being prPferred, snd COY is ~n aromatically bound ficyl halide group, which diacyl halide is polymerizable wi~h at least one aromatic compound of (a~ , and (ii) ~t least one sromatic nucleophilic compound of the formula H-Ar'-H
where -Ar'- is 8 divalent ~romatlc radical such as diphenylether-4,4'-dlyl, 2,7-dibenzofuranediyl, diphenyl-4,4'-diyl, diphenylmethane-4,4'-diyl, naphthalene-diyl, phenanthrenediyl, ~nd the like, and H is an ~romatlcally bound hydrogen atom, which compound is ~-~4605 polymerlzable with at least one diacyl halide of (a)(i~, and (b) ~t least one aromatic monoacyl halide of formula H-Ar"-COY
where -Ar"- is R divalent sromatic radlcal such as diphenylether-4,4'-diyl, diphenylmethane -4,4'-diyl, naphthalene-d-iyl, diphenyl-4,4'-diyl,
2,7-dibenzofuranediyl, and the like, and H is an aromatically bound hydrogen atom, Y is as defined above, ~nd COY is an aromatically bound acyl halide group, which monoacyl hallde is self-polymeriz~ble, and (c) a combination of (a~ and (b).
Specifically, the polyketones may be prepsred by reacting one or more of the following nucleophilic coreactants: diphenyl sulfide, dibenzofuran, thianthrene, phenoxathin, phenodioxin, diphenylene, diphenyl, dibenzodioxine, xanthone, 4,4'-diphenoxybiphenyl, 2,2'-diphenoxybiphenyl, 1,2-diphenoxybenzene, 1,3-diphenoxybenzene, 1,4-diphenoxybenzene, l-phenoxynaphthalene, 1,2-diphenoxynaphthalene, diphenyl ether, 1,5-diphenoxynaphthalene.
Similarly, the following electrophllic aromatic coreactant candidates for polyketone ~ormatlon may be useful: terephthaloyl chloride, isophthaloyl chloride, thio-bls(4,4'-benzoyl chloride), benzophenone-4,4'-dl(carbonyl chloride), oxy-bis(4,4' benzoyl chloride), oxy-bis(3,3'-benzoyl chloride), diphenyl-3,3'-di(carbonyl chloride), carbonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(4,4'-benzoyl chloride), 9~7 sulfonyl-bis(3,3'-benzoyl chloride~, sulfonyl-bis(3,4'-benzoyl chloride), th~o-bis(3,4'-benzoyl chloride), diphenyl-3,4'-di(carbonyl chloride), oxy-bis L 4,4'-(2-chlorobenzoy~ chlorlde)j, naphthalene-1,6-di(carbonyl chloride), naphthalene-1,7-di(carbonyl chloride~, naphthalene-1,5-di~carbonyl chloride), naphthalene-2,6-di(csrbonyl chlorlde), oxy-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)],thio-bis[8,8'-naphthalene-2,2'-di(carbonyl chloride)], 7,7'-binaph~hyl-2,2'-di(carbonyl chloride), diphenyl-4,4'-di(carbonyl chloride), carbonyl-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], sulfonyl-bis[6,6'-naphthalene-2,2'-di(carbonyl chloride)], dibenzofuran-2,7-di(carbonyl chloride) and the like, or the combination of sny of the above.
In addition to the electrophilic aromaeic coreactants carbonyl chloride (phosgene), c~rbonyl dibromide, carbonyl difluoride or oxalyl chloride may be used.
Examples of compounds corresponding to the formula H-Ar"-COY include p-phenoxybenzoyl chloride, p-biphenyloxybenzoyl chloride, 4-(p-phenoxyphenyl) benzoyl chloride, 4-(p-phenoxybenzoyl) benzoyl chloride, 4(p-phenoxyphenoxy) benzoyl chloride
Specifically, the polyketones may be prepsred by reacting one or more of the following nucleophilic coreactants: diphenyl sulfide, dibenzofuran, thianthrene, phenoxathin, phenodioxin, diphenylene, diphenyl, dibenzodioxine, xanthone, 4,4'-diphenoxybiphenyl, 2,2'-diphenoxybiphenyl, 1,2-diphenoxybenzene, 1,3-diphenoxybenzene, 1,4-diphenoxybenzene, l-phenoxynaphthalene, 1,2-diphenoxynaphthalene, diphenyl ether, 1,5-diphenoxynaphthalene.
Similarly, the following electrophllic aromatic coreactant candidates for polyketone ~ormatlon may be useful: terephthaloyl chloride, isophthaloyl chloride, thio-bls(4,4'-benzoyl chloride), benzophenone-4,4'-dl(carbonyl chloride), oxy-bis(4,4' benzoyl chloride), oxy-bis(3,3'-benzoyl chloride), diphenyl-3,3'-di(carbonyl chloride), carbonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(4,4'-benzoyl chloride), 9~7 sulfonyl-bis(3,3'-benzoyl chloride~, sulfonyl-bis(3,4'-benzoyl chloride), th~o-bis(3,4'-benzoyl chloride), diphenyl-3,4'-di(carbonyl chloride), oxy-bis L 4,4'-(2-chlorobenzoy~ chlorlde)j, naphthalene-1,6-di(carbonyl chloride), naphthalene-1,7-di(carbonyl chloride~, naphthalene-1,5-di~carbonyl chloride), naphthalene-2,6-di(csrbonyl chlorlde), oxy-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)],thio-bis[8,8'-naphthalene-2,2'-di(carbonyl chloride)], 7,7'-binaph~hyl-2,2'-di(carbonyl chloride), diphenyl-4,4'-di(carbonyl chloride), carbonyl-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], sulfonyl-bis[6,6'-naphthalene-2,2'-di(carbonyl chloride)], dibenzofuran-2,7-di(carbonyl chloride) and the like, or the combination of sny of the above.
In addition to the electrophilic aromaeic coreactants carbonyl chloride (phosgene), c~rbonyl dibromide, carbonyl difluoride or oxalyl chloride may be used.
Examples of compounds corresponding to the formula H-Ar"-COY include p-phenoxybenzoyl chloride, p-biphenyloxybenzoyl chloride, 4-(p-phenoxyphenyl) benzoyl chloride, 4-(p-phenoxybenzoyl) benzoyl chloride, 4(p-phenoxyphenoxy) benzoyl chloride
3-chlorocarbinyl dlbenzofuran, l-nRphthoyl chloride, 2-naphthoyl chlor~de, ~nd the like.
Preferably, diphenyl ether is reacted with terephthaloyl chloride andJor isophthaloyl chloride.
~24~97 The preferred ~rledel-Crsfts c~t~lysts are aluminum chloride, antimony pentachloride and ferric chloride. Other ~riedel-Cr~fts c~t~lysts, such as ~luminum bromlde, boron trifluoride, zinc chloride, ~ntimony trlchloride, ferric bromide ~nd stannic chloride, can also be used.
The reaction may be carried out over a range of temperstures of from about 0C. to about 16QC. In general, it is preferred to carry out the reaction at a temperature in the range of between 0~
and 30~C. However, in some cases it ls advantageous to carry out the reaction at temperatures ~bove 30~C. or below O~C. The resction is generally carried out at ambient pressure. HoweYer, in some inst~nces i~ may be advantageous to carry out the reaction at pressures gre~ter than atmospheric or at subatmospheric pressures.
The resction is c~rried out in a solven~
system containing at least 50 percent by weight of 1,2-dichloroethane.
The reaction may be carried out ln the presence of a capping ~8ent ~s described in Patent Applicati~n Serial No. 503,030 filed on an even date &S this application in the n~me of L. M~
Maresca and titled, "A Method For Stabilizing Poly~Aryl Ether Ketones)", commonly assigned.
Said Rppllc~ion is dlrected to a method of stabilizlng poly(~ryl ether ketones) by reacting nucleophillc coreact~nts with electrophlllc coreac~ants under heterogeneous Friedel-Crafts polymerizQtion condltlons by adding ~ nucleophilic and/or electrophilic c~pping agent during polymerization.
*corresponds to USP 4,710,562 The nucleophilic cappin~ BgentS ~re of the ~eneral formul~:
~ x ~ y and ~ z -.
wherein x ~s a covslent bond, -O-, -S-, or -CR2-wherein esch R is independently hydrogen, ~n ~lkyl or fluoroalkyl group, prefer~bly of 1 to 10 carbons, phenyl or ~n eiectron withdr~wing group substituted phenyl. Prefer~bly, x is a covalent ~ond, or ~, y i s NC~2, - C ~ 3r - S02 ~
or if x is ~ covalent bond, y can also be hydrogen RS well as sny of the foregoing9 z is h~logen, ~lkyl or alkoxy Specific examples of appropri~te nucleophilic c~pp1ng R~ents are
Preferably, diphenyl ether is reacted with terephthaloyl chloride andJor isophthaloyl chloride.
~24~97 The preferred ~rledel-Crsfts c~t~lysts are aluminum chloride, antimony pentachloride and ferric chloride. Other ~riedel-Cr~fts c~t~lysts, such as ~luminum bromlde, boron trifluoride, zinc chloride, ~ntimony trlchloride, ferric bromide ~nd stannic chloride, can also be used.
The reaction may be carried out over a range of temperstures of from about 0C. to about 16QC. In general, it is preferred to carry out the reaction at a temperature in the range of between 0~
and 30~C. However, in some cases it ls advantageous to carry out the reaction at temperatures ~bove 30~C. or below O~C. The resction is generally carried out at ambient pressure. HoweYer, in some inst~nces i~ may be advantageous to carry out the reaction at pressures gre~ter than atmospheric or at subatmospheric pressures.
The resction is c~rried out in a solven~
system containing at least 50 percent by weight of 1,2-dichloroethane.
The reaction may be carried out ln the presence of a capping ~8ent ~s described in Patent Applicati~n Serial No. 503,030 filed on an even date &S this application in the n~me of L. M~
Maresca and titled, "A Method For Stabilizing Poly~Aryl Ether Ketones)", commonly assigned.
Said Rppllc~ion is dlrected to a method of stabilizlng poly(~ryl ether ketones) by reacting nucleophillc coreact~nts with electrophlllc coreac~ants under heterogeneous Friedel-Crafts polymerizQtion condltlons by adding ~ nucleophilic and/or electrophilic c~pping agent during polymerization.
*corresponds to USP 4,710,562 The nucleophilic cappin~ BgentS ~re of the ~eneral formul~:
~ x ~ y and ~ z -.
wherein x ~s a covslent bond, -O-, -S-, or -CR2-wherein esch R is independently hydrogen, ~n ~lkyl or fluoroalkyl group, prefer~bly of 1 to 10 carbons, phenyl or ~n eiectron withdr~wing group substituted phenyl. Prefer~bly, x is a covalent ~ond, or ~, y i s NC~2, - C ~ 3r - S02 ~
or if x is ~ covalent bond, y can also be hydrogen RS well as sny of the foregoing9 z is h~logen, ~lkyl or alkoxy Specific examples of appropri~te nucleophilic c~pp1ng R~ents are
4 - nitrodiphenyl ether 4 - phenoxybenzophenone 4 - phenoxydiphenyl sulfone ~nisole fluorobenzene chlorobenzene biphenyl toluene.
acetyl chlorlde The electrophilic capping ~gents correspond to the formul~
O O
w ~ C Cl w ~ S -~1 ~f~ 7 g where w = halogen, alkyl, slkoxy, nltro, O ' O
/=~\ " ~'=~ "
or ~ 5 _ o Speciflc ex~mples of these end cepping agents include the following benzoyl chloride p-fluorobenzoyl chloride p-chlorobenzoyl chloride p-methoxybenzoyl chloride benæene sulfonyl chloride p-chlorobenzene sulfonyl chloride p-methylbenzene sulfonyl chloride 4-benzoyl-benzoyl chloride The capping agents may be added anytlme during or after the polymerization re~ction but preferably are added with the resct~nts ~t the beginning of the polymerization reaction.
The polymer of this invention may include mlneral fillers such ~s c~rbonates including chalk, calcite and dolomite; silicates including mic8, talc, woll~stonite; silicon dioxide; glass spheres' glass powders; ~luminum; clay; quartz; and the like. Also, reinforcing fibers such as fiberglsss, carbon fibers, and the like msy be used. The polymers may also include ~dditives such us titsnium dioxide; thermal ~tabilizers, ultr~violet light st~bilizers, plssticizers, ~nd the llke.
The polymers of this invention m~y be fabricated into ~ny desired shape, i.e., moldings, coatings, films or fibers. They are particularly ~6,'~7 - 10-.
desirable for use as electrical lnsulation for electrical conductors.
EXAMPLES
The following examples serve to give specific lllustrations of the practice of this invention but they are not intende~ in any way to limit the scope of this inYention.
Example 1 A 2 liter, 3 neck, round bot~om flask was equipped with a mechanical stirrer, a nitrogen inlet, condenser and a thermometer. The flask was charged with 14.21 g (0.07 moles) of terephthaloyl chloride, 6.09 g (0.030 moles) of isophthaloyl chloride, 17.01 g (0.100 moles) of diphenyl ether and 700 mls of 1,2-dichloroethane. This solution was cooled to 5C in an ice water bath. Aluminum chloride (34.76 g~ 0.260 moles) was added in portions while maintainlng the temperature below 10C. The resul~ing reaction mixture was held at
acetyl chlorlde The electrophilic capping ~gents correspond to the formul~
O O
w ~ C Cl w ~ S -~1 ~f~ 7 g where w = halogen, alkyl, slkoxy, nltro, O ' O
/=~\ " ~'=~ "
or ~ 5 _ o Speciflc ex~mples of these end cepping agents include the following benzoyl chloride p-fluorobenzoyl chloride p-chlorobenzoyl chloride p-methoxybenzoyl chloride benæene sulfonyl chloride p-chlorobenzene sulfonyl chloride p-methylbenzene sulfonyl chloride 4-benzoyl-benzoyl chloride The capping agents may be added anytlme during or after the polymerization re~ction but preferably are added with the resct~nts ~t the beginning of the polymerization reaction.
The polymer of this invention may include mlneral fillers such ~s c~rbonates including chalk, calcite and dolomite; silicates including mic8, talc, woll~stonite; silicon dioxide; glass spheres' glass powders; ~luminum; clay; quartz; and the like. Also, reinforcing fibers such as fiberglsss, carbon fibers, and the like msy be used. The polymers may also include ~dditives such us titsnium dioxide; thermal ~tabilizers, ultr~violet light st~bilizers, plssticizers, ~nd the llke.
The polymers of this invention m~y be fabricated into ~ny desired shape, i.e., moldings, coatings, films or fibers. They are particularly ~6,'~7 - 10-.
desirable for use as electrical lnsulation for electrical conductors.
EXAMPLES
The following examples serve to give specific lllustrations of the practice of this invention but they are not intende~ in any way to limit the scope of this inYention.
Example 1 A 2 liter, 3 neck, round bot~om flask was equipped with a mechanical stirrer, a nitrogen inlet, condenser and a thermometer. The flask was charged with 14.21 g (0.07 moles) of terephthaloyl chloride, 6.09 g (0.030 moles) of isophthaloyl chloride, 17.01 g (0.100 moles) of diphenyl ether and 700 mls of 1,2-dichloroethane. This solution was cooled to 5C in an ice water bath. Aluminum chloride (34.76 g~ 0.260 moles) was added in portions while maintainlng the temperature below 10C. The resul~ing reaction mixture was held at
5-10C for 6 hours. After ~30 minutes a precipitate formed. At the end of 6 hours the ice bsth was removed and the reaction mixture was allowed to warm to ambient temperatures ~~25C) where i~ was held for an additlonal 16 hours. The reaction mixture was poured into 3 liters of ice water containin~ 100 ml of concentrated hydrochloric acid. The resulting three phase system was heated to ~85C to distill the 1,2-dichloroethane. The polymer was lsolated by filtration, washed with wate~ (2x500 ml) and methanol ~2xS00 ml) and dried in a vacuum oven ~t 100C. The product had r reduced YiscoSity of 1.62 dl~ as measured in concentrated sulfuric scid at 25DC and a concentration of l g/lO0 ml.
_mparative Examples A-M
Example 1 was repeated using ~ variety of solvents, including those well known to be useful in Friedel-Crafts reactions. The results are summarized in Table l.
TABLE l Reduced Viscosity of Final Example _ Solvent Polymer (dl/~) A Carbon Disulfide 0.06 B l,l,l-Trichloroeth~ne 0.07 C Methylene Chloride 0.50 D Methylene Ghloridel 0.92 E Csrbon Tetr~chloride 0.07 F Trichloroethylene 0.17 Nitrobenzene 0.18 H O-Dichlorobenzene 0.31 I O-Dichlorobenzene2 0.47 J O-Dichlorobenzene3 0.51 K 1,2,4-Trichlorobenzene 0.09 L Trichlorofluorometh~ne 0.05 M 1,1,2-Trichlorotrifluoroethsne 0.04 llt excess of dlphenyl ether was used 2Four hours at 80C instead of 16 hours at 25C
3Six hours at 80C instead of 16 h~urs at 25C
Although relatively high molecular weight polymers can be prepared using me~hylene chloride, this solYent participates in the reaction resulting in ~lkylation of ehe polymer backbone ~s a ma~or side product. Excess diphenyl ether is needed to obtain high molecular weight product because of this side resction which consumes diphenyl ether and disrupts the reaction stoichiometry. These alkylated side products lead to polymer instability at elevated temperatures.
Examples 2 -7 Example 1 was repe~ted except tha~ a capping agent was added ~o control the molecular weight of polymer. The stoich~ometry of the primary reactants is shown in the equation:
O
~e-t~
Gl-C ~ ~ t ~l+X) ~ O ~ ~ 2X ~ C-Cl o 1,2 dichl~r~ethane 5 - 25'~
W ~ ~ O--~' C ~
Reduced viscosity as a function of the end c~pplng sgent concentration is sh~wn in Table 2.
Terephthaloyl Chlorlde/
Isophthaloyl Reduced Example Chloride X _ Viscosity 2 90/10 .003 1.21 3 100/0 .003 1.46 4 95/5 .005 .83 9~/5 .015 .58
_mparative Examples A-M
Example 1 was repeated using ~ variety of solvents, including those well known to be useful in Friedel-Crafts reactions. The results are summarized in Table l.
TABLE l Reduced Viscosity of Final Example _ Solvent Polymer (dl/~) A Carbon Disulfide 0.06 B l,l,l-Trichloroeth~ne 0.07 C Methylene Chloride 0.50 D Methylene Ghloridel 0.92 E Csrbon Tetr~chloride 0.07 F Trichloroethylene 0.17 Nitrobenzene 0.18 H O-Dichlorobenzene 0.31 I O-Dichlorobenzene2 0.47 J O-Dichlorobenzene3 0.51 K 1,2,4-Trichlorobenzene 0.09 L Trichlorofluorometh~ne 0.05 M 1,1,2-Trichlorotrifluoroethsne 0.04 llt excess of dlphenyl ether was used 2Four hours at 80C instead of 16 hours at 25C
3Six hours at 80C instead of 16 h~urs at 25C
Although relatively high molecular weight polymers can be prepared using me~hylene chloride, this solYent participates in the reaction resulting in ~lkylation of ehe polymer backbone ~s a ma~or side product. Excess diphenyl ether is needed to obtain high molecular weight product because of this side resction which consumes diphenyl ether and disrupts the reaction stoichiometry. These alkylated side products lead to polymer instability at elevated temperatures.
Examples 2 -7 Example 1 was repe~ted except tha~ a capping agent was added ~o control the molecular weight of polymer. The stoich~ometry of the primary reactants is shown in the equation:
O
~e-t~
Gl-C ~ ~ t ~l+X) ~ O ~ ~ 2X ~ C-Cl o 1,2 dichl~r~ethane 5 - 25'~
W ~ ~ O--~' C ~
Reduced viscosity as a function of the end c~pplng sgent concentration is sh~wn in Table 2.
Terephthaloyl Chlorlde/
Isophthaloyl Reduced Example Chloride X _ Viscosity 2 90/10 .003 1.21 3 100/0 .003 1.46 4 95/5 .005 .83 9~/5 .015 .58
6 95/5 .025 .54
7 90J10 .025 .49
8 100/0 .025 .55
9 90~10 .050 .36 ~0/10 .Q50 .36 11 100/0 .05~ .39 12 100/0 .OS0 .39
Claims (8)
1. An improved process for preparing poly(aryl ether ketone) by reacting nucleophillc coreactants with electrophilic coreactants under Friedel-Crafts polymerization conditions, wherein the improvement comprises carrying out the process in a solvent comprising 1,2-dichloroethane.
2. A process as defined in claim 1 wherein the poly (aryl ether ketone) is prepared by reacting one or more of the following nucleophilic coreactants: diphenyl sulfide, dibenzofuran, thianthrene, phenoxathin, phenodioxin, diphenylene, diphenyl, 4,4'-diphenoxybiphenyl, 2,2'-diphenoxylbiphenyl, 1,2-diphenoxybenzene, 1,3-diphenoxybenzene, 1,4-diphenoxybenzene, 1-phenoxynaphthalene, 1,2-diphenoxynaphthalene, diphenyl ether, or 1,5-diphenoxynaphthalene.
3. A process as defined in claim 1 wherein the poly (aryl ether ketone) is prepared by reacting one or more of the following electrophilic coreactants: phosgene, carbonyl difluoride, terephthaloyl chloride, isophthaloyl chloride, thio-bis(4,4'-benzoyl chloride), benzophenone-4,4'-di(carbonyl chloride), oxy-bis(4,4'-benzoyl chlorlde), oxy-bis(3,3'-benzoyl chloride), diphenyl-3,3'-dl(carbonyl chloride), carbonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(4,4'-benzoyl chloride), sulfonyl-bis(3,3'-benzoyl chloride), sulfonyl-bis(3,4'-benzoyl chloride), thio-bis(3,4'-benzoyl chloride), diphenyl-3,4'-di(carbonyl chloride), diphenyl-4,4'-di(carbonyl chloride), oxy-bis[4,4'-(2-chlorobenzoyl chloride)], naphthalene-1,5-di(carbonyl chloride), naphthalene-1,6-di(carbonyl chloride), naphthalene-1,7-di(csrbonyl chloride), naphthalene-2,6-di(carbonyl chloride), oxy-bis[7,7'-naphthalene-2,2'-di(carbonyl chloride)], thio-bis[8,8'-naphthalene-2,2'-di(carbonyl chloride)], 7,7'-binaphthyl-2'-di(carbonyl chloride), carbonyl-bis[7,7'-naphthalene-2,2'- di(carbonyl chloride)], sulfonyl-bis[6,6'-naphthalene-2,2'-di(carbonyl chloride)], or dibenzofuran-2,7-di(carbonyl chloride).
4. A process defined in claim 1 wherein the reactant and/or correactant is selected from 4-phenoxybenzoyl chloride, 1-phenoxy-1-napthalene carbonyl chloride, 4-phenoxy-4'-chlorocarbonyl diphenyl or 4-phenoxy-3'-chlorocarbonyl diphenyl ether.
5. A process as defined in claim 1 wherein diphenyl ether is reacted with terephthaloyl chloride and/or isophthaloyl chloride.
6. A process as defined in claim 1 wherein the process is carried out in the presence of a Freidel-Crafts catalyst selected from aluminum chloride, antimony pentachloride or ferric chloride.
7. A process as defined in claim 1 wherein the process is carried out at a temperature of from about 0°C to about 25°C.
8. An improved process for preparing a poly (aryl ether ketone) by reacting diphenyl ether with terephthaloyl chloride and/or isophthaloyl chloride under Friedel-Crafts polymerization conditions, wherein the improvement comprises carrying out the process in a solvent comprising 1,2-dichloroethane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71011985A | 1985-03-11 | 1985-03-11 | |
| US710,119 | 1985-03-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1246297A true CA1246297A (en) | 1988-12-06 |
Family
ID=24852705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000503032A Expired CA1246297A (en) | 1985-03-11 | 1986-02-28 | Process for preparing poly(aryl ether ketones) |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS61211336A (en) |
| CA (1) | CA1246297A (en) |
| DE (1) | DE3607902A1 (en) |
| GB (1) | GB2172294A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8725886D0 (en) * | 1987-11-04 | 1987-12-09 | Raychem Ltd | Poly(ar-lene ether ketones) |
| GB8726884D0 (en) * | 1987-11-17 | 1987-12-23 | Raychem Ltd | Poly(arylene ether ketones) |
| GB8904410D0 (en) * | 1989-02-27 | 1989-04-12 | Ici Plc | Aromatic polymers |
| US4918237A (en) * | 1989-03-13 | 1990-04-17 | E. I. Du Pont De Nemours And Company | Process for the manufacture of 1,4-bis(4-phenoxybenzoyl)benzene with certain metal-containing catalysts |
| WO1991013929A1 (en) * | 1990-03-16 | 1991-09-19 | Asahi Kasei Kogyo Kabushiki Kaisha | Noncrystalline polymers and production thereof |
| GB2364319B (en) | 2000-07-06 | 2003-01-15 | Gharda Chemicals Ltd | Melt processible polyether ether ketone polymer |
| CN103665368B (en) * | 2013-11-28 | 2017-01-11 | 张家港祥成医用材料科技有限公司 | Method for low-temperature synthesis of polyaryletherketone resin on nanometer/micrometer-scale inorganic seedbed |
| EP3404011B1 (en) | 2017-05-18 | 2020-08-26 | Arkema France | Dissociation of a 1,4-bis(4-phenoxybenzoyl)benzene-lewis acid-complex in an aqueous solution |
| EP3404012B1 (en) | 2017-05-18 | 2020-09-09 | Arkema France | Ripening of 1,4-bis (4-phenoxybenzoyl)benzene |
| ES2829265T3 (en) * | 2017-05-16 | 2021-05-31 | Arkema France | Method for making 1,4-bis (4-phenoxybenzoyl) benzene at an elevated temperature |
| KR102262524B1 (en) * | 2017-11-16 | 2021-06-07 | 한화솔루션 주식회사 | Method for preparing poly ether ketone ketone |
| EP3650433B1 (en) | 2018-11-09 | 2024-04-24 | Arkema France | Method for manufacturing 1,4-bis (4-phenoxybenzoylbenzene) at an elevated temperature |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3516966A (en) * | 1968-02-05 | 1970-06-23 | Du Pont | Polyketone copolymers |
| GB1340709A (en) * | 1970-06-10 | 1973-12-12 | Du Pont | Process for producing crystalline copolyketone films and insulated electrical conductors |
| DE2266022C2 (en) * | 1971-02-16 | 1987-11-19 | Raychem Corp., Menlo Park, Calif., Us | |
| US3791890A (en) * | 1972-02-18 | 1974-02-12 | Du Pont | Granualr polyketone preparation |
| BR8406499A (en) * | 1983-03-31 | 1985-03-12 | Raychem Corp | PREPARATION OF AROMATIC POLYMERS |
| DE3472262D1 (en) * | 1983-09-29 | 1988-07-28 | Mitsubishi Chem Ind | Process for producing aromatic polyether ketones and polythioether ketones |
-
1986
- 1986-02-28 CA CA000503032A patent/CA1246297A/en not_active Expired
- 1986-03-10 DE DE19863607902 patent/DE3607902A1/en not_active Ceased
- 1986-03-10 JP JP5073786A patent/JPS61211336A/en active Pending
- 1986-03-10 GB GB08605837A patent/GB2172294A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61211336A (en) | 1986-09-19 |
| GB8605837D0 (en) | 1986-04-16 |
| DE3607902A1 (en) | 1986-09-11 |
| GB2172294A (en) | 1986-09-17 |
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