POLYFUNCTIONAL POLY(ARYLENE ETHER) METHOD
BACKGROUND OF THE INVENTION
[0001] Poly(arylene ether) resins and their blends with styrenic resins are used
in many commercial applications that benefit from their temperature resistance,
stiffness, impact strength, and dielectric properties. Conventional poly(arylene ether)
resins have intrinsic viscosities of about 0.3 to about 0.6 deciliter per gram, as
measured in chloroform at 25°C. Conventional poly(arylene ether) resins also have,
on average, about one terminal hydroxy group per polymer chain. Recently, some
new applications for poly(arylene ether) resins, including compositions for printed
circuit board fabrication, have created a need for poly(arylene ether) resins with lower
intrinsic viscosities and more than one terminal hydroxy group per polymer chain.
However, known synthesis methods are not suitable for the preparation of such low
intrinsic viscosity, high functionality poly(arylene ether) resins. For example, as
described below, the present inventors found that a conventional method of using an
aqueous solution of chelating agent to extract polymerization catalyst metal ion from
an organic solution of poly(arylene ether) resin resulted in formation of dispersions
that made it difficult to separate the poly(arylene ether) from the polymerization
catalyst. There is therefore a need for new poly(arylene ether) synthesis methods that
avoid the formation of a dispersion during purification of poly(arylene ether) resins
having low intrinsic viscosity and high functionality.
BRIEF DESCRIPTION OF THE INVENTION
[0002] The above-described and other drawbacks are alleviated by a method
of preparing a polyfunctional poly(arylene ether) resin, comprising: oxidatively
copolymerizing a monohydric phenol and a polyhydric phenol in an aromatic
hydrocarbon solvent in the presence of a catalyst comprising a metal ion and a
nitrogen-containing ligand to form a solution comprising a polyfunctional
poly(arylene ether) having an intrinsic viscosity of about 0.04 to about 0.3 deciliter per
gram at 25°C in chloroform; and contacting the polyfunctional poly(arylene ether)
solution with an aqueous solution of a chelating agent to extract the metal ion from
the solution; wherein the chelating agent and metal ion are present in a molar ratio of
about 1.0 to about 1.5.
[0003] Other embodiments, including particular methods of preparing
polyfunctional poly(arylene ether) resins, are described in detail, below.
DETAILED DESCRIPTION OF THE INVENTION
[0004] One embodiment is a method of preparing a polyfunctional
poly(arylene ether) resin, comprising: oxidatively copolymerizing a monohydric
phenol and a polyhydric phenol in an aromatic hydrocarbon solvent in the presence of
a catalyst comprising a metal ion and a nitrogen-containing ligand to form a solution
comprising a polyfunctional poly(arylene ether) having an intrinsic viscosity of about
0.04 to about 0.3 deciliter per gram at 25°C in chloroform; and contacting the
polyfunctional poly(arylene ether) solution with an aqueous solution of a chelating
agent to extract the metal ion from the solution; wherein the chelating agent and metal
ion are present in a molar ratio of about 1.0 to about 1.5. In the process of research on
methods of preparing poly(arylene ether) resins having low intrinsic viscosity and
high functionality, the present inventors discovered that conventional methods of
extracting catalyst metal ion from a solution of the poly(arylene ether) resulted in the
formation of a dispersion that made it difficult to separate the catalyst metal ion from
the poly(arylene ether). In particular, when a poly(arylene ether) having an intrinsic
viscosity of 0.04 to about 0.3 deciliter per gram and a functionality of at least about
1.5 terminal hydroxyl groups, on average, per chain, was synthesized by metal-
catalyzed polymerization of phenolic monomers in an aromatic solvent, and when the
resulting solution of poly(arylene ether) was treated with an aqueous solution of a
chelating agent to remove the catalyst metal ion, the agitated mixture of the
poly(arylene ether) solution and the aqueous chelating agent solution formed a
dispersion that did not readily phase separate when agitation was ceased. Thus, the
aqueous solution containing the catalyst metal ion and the organic solution containing
the poly(arylene ether) could not readily be separated. After extensive research, the
present inventors discovered the formation of a dispersion could be avoided by
reducing the concentration of chelating agent in the aqueous solution. It was
previously thought that such a reduction in the chelating agent concentration would
lead to insufficient removal of catalyst metal ion from the poly(arylene ether), but it
was surprisingly discovered that the reduced chelating agent concentrations both
avoided the dispersion problem and adequately reduced the concentration of catalyst
metal ion in the isolated poly(arylene ether) resin. Specifically, using the chelating
agent in an amount of about 1.0 to about 1.5 moles per mole of catalyst metal ion
avoided dispersion formation while removing all but a few parts per million by weight
of catalyst metal from the poly(arylene ether) resin.
[0005] The method comprises oxidatively copolymerizing a monohydric
phenol and a polyhydric phenol. The monohydric phenol is a compound having a
single phenolic hydroxyl group. In one embodiment, the monohydric phenol has the
structure
(Formula-Removed)
wherein each occurrence of Q1 is independently halogen, primary or secondary C1-C12
alkyl, C1-C12 alkenyl, C3-C12 alkenylalkyl, C2-C12 alkynyl, C3-C12 alkynylalkyl, C1-C12
aminoalkyl, C1-C12 hydroxyalkyl, C6-C12 aryl (including phenyl), C1-C12 haloalkyl,
C1-C12 hydrocarbonoxy, C1-C12 halohydrocarbonoxy wherein at least two carbon
atoms separate the halogen and oxygen atoms, or the like; and wherein each
occurrence of Q2 is independently hydrogen, halogen, primary or secondary C1-C12
alkyl, C1-C12 alkenyl, C3-C12 alkenylalkyl, C2-C12 alkynyl, C3-C12 alkynylalkyl, C1-C12
aminoalkyl, C1-C12 hydroxyalkyl, C6-C12 aryl (including phenyl), C1-C12 haloalkyl,
C1-C12 hydrocarbonoxy, C1-C12 halohydrocarbonoxy wherein at least two carbon
atoms separate the halogen and oxygen atoms, or the like. In one embodiment, each
occurrence of Q1 is independently primary or secondary C1-C12 alkyl, C1-C12 alkenyl,
C3-C12 alkenylalkyl, or C3-C12 aryl; and each occurrence of Q2 is independently
hydrogen or primary or secondary C1-C12 alkyl. In one embodiment, the monohydric
phenol is selected from 2,6-dimethylphenol, 2,3,6-trimethylphenol, and mixtures
thereof.
[0006] The polyhydric phenol is a compound having two or more phenolic
hydroxy groups. The polyhydric phenol preferably comprises two or more arene
rings, each with at most one phenolic hydroxy group. In one embodiment, the
polyhydric phenol comprises 2 to about 8 phenolic hydroxy groups. In one
embodiment, the polyhydric phenol comprises a dihydric phenol (i.e., a compound
having two phenolic hydroxyl groups).
[0007] The dihydric phenol may have the structure
(Formula-Removed)
wherein each occurrence of R1 and R2 is independently hydrogen, halogen, primary or
secondary C1-C12 alkyl, C1-C12 alkenyl, C1-C12 alkynyl, C1-C12 aminoalkyl, C1-C12
hydroxyalkyl, C1-C12 aryl (including phenyl), • C1-C12 haloalkyl, C1-C12
hydrocarbonoxy, C1-C12 halohydrocarbonoxy wherein at least two carbon atoms
separate the halogen and oxygen atoms, or the like; z is 0 or 1; and Y is selected from
(Formula-Removed)
wherein each occurrence of R3-R6 is independently hydrogen or C1-C12 hydrocarbyl.
In the embodiment in which Y is
(Formula-Removed)
the wavy lines signify that R4 and R5 may be either cis or trans with respect to each
other. In one embodiment, the dihydric phenol has the structure above, wherein each
occurrence of R1 is methyl, each occurrence of R2 and R3 is independently hydrogen
or methyl. Suitable dihydric phenols include, for example, l,l-bis(3,5-dimethyl-4-
hydroxyphenyl)ethane, 1,1 -bis(3-chloro-4-hydroxyphenyl)ethane, 1,1 -bis(3-methyl-4-
hydroxyphenyl)-ethane, 1,2-bis(4-hydroxy-3,5-dimethyl phenyl)-1,2-diphenylethane,
l,2-bis(3-methyl-4-hydroxyphenyl)-l,2-diphenylethane, l,2-bis(3-methyl-4-
hydroxyphenyl)ethane, 2,2'-binaphthol, 2,2'biphenol, 2,2'-dihydroxy-4,4'-
dimethoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-
dihydroxybenzophenone, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-
bromo-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-
bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane, 1,1 -bis(3,5-dimethyl-4-hydroxyphenyl)-1 -phenylethane, 1,1-
bis(3-chloro-4-hydroxyphenyl)-1 -phenylethane, 1,1 -bis(3-methyl-4-hydroxyphenyl)-1 -
phenylethane, 2,2-bis(4-hydroxy-3,5-dimethyl phenyl)-1-phenylpropane, 2,2-bis(4-
hydroxy-3,5-dimethyl phenyl)hexane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)pentane,
2,2-bis(3-methyl-4-hydroxynaphthyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)-1 -
phenylpropane, 2,2-bis(3-methyl-4-hydroxyphenyl)hexane, 2,2-bis(3-methyl-4-
hydroxyphenyl)pentane, 2,2'-methylenebis(4-methylphenol), 2,2'-methylenebis[4-
methyl-6-(l -methylcyclohexyl)phenol], 3,3' ,5,5' -tetramethyl-4,4' -biphenol, 3,3' -
dimethyl-4,4'-biphenol, bis(2-hydroxyphenyl)-methane, bis(4-hydroxy-2,6-dimethyl-
3-methoxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-
4-hydroxyphenyl)methane, bis-(4-hydroxy-3,5-dimethyl phenyl)-cyclohexylmethane,
bis(4-hydroxy-3,5-dimethyl phenyl)phenylmethane, bis(3-methyl-4-
hydroxyphenyl)cyclohexylmethane, bis(3-methyl-4-hydroxyphenyl)methane, bis(3,5-
dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)phenylmethane,
2,2',3,3',5,5'-hexamethyl-4,4'-biphenol, octafluoro-4,4'-biphenol, 2,3,3',5,5'-
pentamethyl-4,4'-biphenol, 1,1 -bis(3,5-dibromo-4-hydroxyphenyl)cyclohexane 1,1-
bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, bis(3-methyl-4-
hydroxyphenyl)cyclohexane tetrabromobiphenol, tetrabromobisphenol A,
tetrabromobisphenol S, 2,2'-diallyl-4,4'-bisphenol A, 2,2'-diallyl-4,4'-bisphenol S,
3,3\5,5'-tetramethyl-4,4'-bisphenol sulfide, 3,3'-dimethyl bisphenol sulfide,
3,3',5,5'-tetramethyl-4,4'-bisphenol sulfone, and combinations thereof. In one
embodiment, the dihydric phenol comprises 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane, sometimes referred to as "tetramethyl bispheno! A".
[0008] The polyhydric phenol may comprise more than two phenolic hydroxy
groups. In one embodiment, the polyhydric phenol comprises 3 or 4 phenolic hydroxy
groups. Suitable polyhydric phenols comprising three or more phenolic hydroxy
groups include, for example, l,l,l-tris(3,5-dimethyl-4-hydrxyphenyl)ethane 1,1,1-
tris(3 -methyl-4-hydroxyphenyl)ethane, 1,3,5 -tris(3,5 -dimethyl-4-hydroxyphenyl-1 -
keto)benzene, 1,3,5 -tris(3,5 -dimethyl-4hydroxyphenyl-1 -isopropylidene)benzene,
2,2,4,4-tetrakis(3-methyl-4hydroxyphenyl)pentane, 2,2,4.4-tetrakis(3,5-dimethyl-4-
hydroxyphenyl)pentane, 1,1,4,4-tetrakis(3 -methyl-4-hydroxyphenyl)cyclohexane,
l,l,4,4-tetrakis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, l,3,5-tris(3,5-dimethyl-4-
hydroxyphenyl)benzene, 1,3,5-tris(3-methyl-4-hydroxyphenyl)benzenf!, 2,6-bis(2-
hydroxy-5-methylbenzyl)-4-methyl phenol, 4,6-dimethyl-2,4,6-tris(4-hydroxy-3-
methylphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxy-3,5-dimethylphenyl)-2-
heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxy-3 -methylphenyl)heptane, 4,6-dimethyl-
2,4,6-tris(4-hydroxy-3-methylphenyl)heptane, 2,4-bis(4-hydroxy-3-
methylphenylisopropyl)phenol, 2,4-bis(4-hydroxy-3,5-
dimethylphenylisopropyl)phenol, tetrakis(4-hydroxy-3-methylphenyl)methane,
tetrakis(4-hydroxy-3,5-dimethylphenyl)methane, tetrakis(4-[4-hydroxy-3-
methylphenylisopropyl]-phenoxy)methane, tetrakis(4-[4-hydroxy-3,5-
dimethylphenylisopropyl]-phenoxy)methane, and combinations thereof. In one
embodiment, the polyhydric phenol comprises a dihydric phenol and a polyhydric
phenol comprising 3 to about 8 phenolic hydroxy groups.
[0009] In one embodiment, the monohydric phenol and the polyhydric phenol
are copolymerized in a mole ratio of about 3 to about 110. Within this range, the ratio
may be at least about 5, or at least about 7. Also within this range, the ratio may be up
to about 50, or up to about 25. Using such a ratio helps ensure that the target intrinsic
viscosity is achieved.
[0010] The method comprises copolymerizing the monohydric phenol and the
polyhydric phenol in an aromatic hydrocarbon solvent. Suitable aromatic
hydrocarbon solvents include, for example, benzene, toluene, xylenes, and the like,
and combinations thereof. In one embodiment, the aromatic hydrocarbon solvent
comprises toluene. In addition to the aromatic hydrocarbon solvent, the solvent may,
optionally, further comprise a C3-C8 aliphatic alcohol that is a poor solvent for the
poly(arylene ether), such as, for example, n-propanol, isopropanol, n-butanol, t-
butanol, n-pentanol, and the like, and combinations thereof. A preferred C3-C8
aliphatic alcohol is n-butanol. The solvent may further comprise, in addition to a C^-
C18 aromatic hydrocarbon and a C3-C8 aliphatic alcohol, methanol or ethanol, which
act as an anti-solvent for the poly(arylene ether). The C3-C18 aromatic hydrocarbon,
the C3-C8 aliphatic alcohol, and the methanol or ethanol may be combined in a wide
range of proportions, but it may be preferred that the solvent comprise at least about
50 weight percent of the C3-C8 aromatic hydrocarbon.
[0011] Although there is no particular limit on the concentrations of the
monohydric phenol and the polyhydric phenol in the aromatic hydrocarbon solvent, it
is preferred to achieve a balance between the increased efficiency of higher monomer
concentrations and the easy-to-handle solution viscosities associated with lower
monomer concentrations. In one embodiment, the monohydric phenol, the polyhydric
phenol, and the solvent are used in amounts such that the ratio of the total weight of
the monohydric phenol and the polyhydric phenol to the total weight of the
monohydric phenol, the polyhydric phenol, and the solvent is about 0.1:1 to about
0.5:1. Within this range, the ratio may be at least about 0.2:1, or at least about 0.23:1,
or at least about 0.26:1. Also within this range, the ratio may be up to about 0.4:1, or
up to about 0.37:1, or up to about 0.34:1.
[0012] The method comprises oxidatively copolymerizing the monohydric
phenol and the polyhydric phenol in an aromatic hydrocarbon solvent in the presence
of a catalyst comprising a metal ion and a nitrogen-containing ligand. In one
embodiment, the catalyst metal ion is selected from ions of copper, manganese,
cobalt, iron, and combinations thereof. In one embodiment, the catalyst metal ion
comprises copper ion. In one embodiment, the concentration of the catalyst metal ion
may be such that the ratio of total moles of monomer (i.e., moles of monohydric
phenol plus moles of polyhydric phenol) to moles of catalyst metal ion may be about
100:1 to about 10,000:1. Within this range, the ratio may be at least about 300:1, or at
least about 600:1. Also within this range, the ratio may be up to about 6,000:1, or up
to about 3,000:1.
[0013] In addition to the metal ion, the copolymerization catalyst comprises a
nitrogen-containing ligand. The nitrogen-containing ligand may include, for example,
alkylenediamine ligands, primary monoamines, secondary monoamines, tertiary
monoamines, aminoalcohols, oximes, oxines, cyanide, and the like, and combinations
thereof.
[0014] Suitable alkylenediamine ligands include those having the formula
(Formula-Removed)
wherein Ra is a substituted or unsubstituted divalent residue wherein two or three
aliphatic carbon atoms form the closest link between the two diamine nitrogen atoms;
and each Rb is independently hydrogen or C1-C8 alkyl. Preferred alkylenediamine
ligands include those in which Ra is ethylene (-CH2CH2-) or trimethylene
(-CH2CH2CH2-), and each Rb is independently hydrogen, isopropyl, or a C4-C8
alpha-tertiary alkyl group. Highly preferred alkylenediamine ligands include
N,N'-di-t-butylethylenediamine and N,N,N',N'-tetramethyl-1,3-diaminopropane.
[0015] Suitable primary monoamines include C3-C12 primary alkylamines,
such as, for example, n-propylamine, i-propylamine, n-butylamine, sec-butylamine,
t-butylamine, n-penylamine, n-hexylamine, cyclohexylamine, combinations
comprising at least one of the foregoing primary monoamines, and the like. A highly
preferred primary monoamine is n-butylamine.
[0016] Suitable secondary monoamines include secondary monoamines
having the structure (Rc)(Rd)NH, wherein Rc and Rd are, each independently a C3-C11
alkyl group, with the proviso that Rc and Rd collectively have a total of four to twelve
carbon atoms. Examples of secondary monoamines include di-n-propylamine, n-
propyl-n-butylamine, di-n-butylamine, d-t-butylamine, n-butyl-n-penylamine, di-n-
hexylamine, and the like, with di-n-butylamine being preferred.
[0017] Suitable tertiary monoamines include tertiary monoamines having the
structure (Re)(Rf)(Rg)N, wherein Re and Rf and Rg are each independently a C1-C16
alkyl group, with the proviso that Re and Rf and R8 collectively have a total of four to
eighteen carbon atoms. Examples of tertiary monoamines include triethylamine, tri-n-
propylamine, tri-n-butylamine, dimethyl-n-butylamine, dimethyl-n-penylamine,
diethyl-n-butylamine, tricyclohexylamine, and the like. In addition, cyclic tertiary
amines, such as pyridine, alpha-collidine, gamma-picoline, and the like, can be used.
Highly preferred tertiary monoamines include dimethyl-n-butylamine. Additional
primary, secondary, and tertiary amines are described in U.S. Patent Nos. 3,306,874
and 3,306,875 to Hay.
[0018] Suitable aminoalcohols include C4-C12 aminoalcohols having one
nitrogen atom and an alcohol oxygen, wherein at least two carbon atoms separate the
amino nitrogen and the alcohol oxygen. Examples of aminoalcohols include N,N-
diethylethanolamine, 4-butanolamine, N-methyl-4-butanolamine, diethanolamine,
triethanolamine, N-phenyl-ethanolamine, and the like, and combinations comprising
at least one of the foregoing aminoalcohols. Highly preferred aminoalcohols include
triethanolamine and N-phenyl-ethanolamine.
[0019] Suitable oximes include benzoin oxime (2-Hydroxy-2-
phenylacetophenone oxime), 2-phenyl-2-hydroxybutan-3-one oxime, 2-salicyl-
aldoxime, and combinations thereof.
[0020] Suitable oxines include those having the formula
(Formula-Removed)

wherein R'-R6 are each independently hydrogen, halogen, hydroxyl, nitro, amino,
C1-C6 alkyl, or C1-C6 alkoxyl. Examples of oxines include oxine, 5-methyloxine,
5-hydroxyoxine, 5-nitroxine, 5-aminoxine, 2-methyloxine, and the like, and
combinations comprising at least one of the foregoing oxines. Highly preferred
oxines include oxine and 5-methyloxine.
[0021] The alkylenediamine ligands, primary monoamines, secondary
monoamines, aminoalcohols, and oxines, when present, may be used at about 0.01 to
about 25 moles per 100 moles of monohydric phenol. The tertiary monoamines may
be used at about 0.1 to about 1,500 moles per 100 moles of monohydric phenol.
[0022] In addition to the metal ion and the nitrogen-containing ligand, the
catalyst may, optionally, further include a halide ion such as chloride, bromide, or
iodide. When employed, halide ions may be supplied to the reaction mixture in the
form of an alkali metal salt or an alkaline earth metal salt at a concentration of about
0.1 mole to about 150 moles per 100 moles total of phenolic monomer.
[0023] In one embodiment, the nitrogen-containing ligand is selected from
dibutylamine, dimethylbutylamine, N,N'-di-t-butylethylenediamine, pyridine, and
combinations thereof. In one embodiment, the complex metal catalyst comprises
copper ion, a secondary alkylenediamine ligand, a secondary monoamine, and a
tertiary monoamine. In one embodiment, the complex metal catalyst comprises
copper ion, N,N'-di-t-butylethylenediamine, di-n-butylamine, and dimethyl-n-
butylamine.
[0024] Various modes of addition of the monohydric phenol and the
polyhydric phenol to the copolymerization mixture are possible. In one embodiment,
all of the monohydric phenol and all of the polyhydric phenol are added to the reactor
before initiating polymerization. In another embodiment, all of the polyhydric phenol
is added to the reactor before initiating polymerization, and a portion of the
monohydric phenol is added to the reaction before initiating polymerization, such that
the molar ratio of monohydric phenol to polyhydric phenol is about 0.1 to about 30
before initiating polymerization. Within this range, the ratio may be at least about 0.5,
or at least about 1. Also within this range, the ratio may be up to about 20, or up to
about 10.
[0025] In another embodiment, a portion of the monohydric phenol and a
portion of the polyhydric phenol are added to the reactor before initiating
polymerization, and the remainder of the monohydric phenol and the remainder of the
polyhydric phenol are added to the reactor after initiating polymerization.
[0026] In one embodiment, during copolymerization, the reaction temperature
may be maintained at about 20 to about 80°C. Within this range, the reaction
temperature may be at least about 30°C, or at least about 40°C. Also within this
range, the reaction temperature may be up to about 70°C, or up to about 60°C.
Different temperatures may be used at different stages of the reaction.
[0027] The polymerization reaction time will depend on factors including the
identities of the monohydric and polyhydric phenol, the solvent, the total monomer
concentration, the catalyst type and concentration, and the oxygen concentration. In
one embodiment, polymerization reaction times are about 0.5 to about 5 hours.
[0028] In one embodiment, during copolymerization, an oxygen flow of about
0.1 to about 3 moles O2 per hour per total moles of monohydric phenol and polyhydric
phenol may be maintained. Within this range, the oxygen flow may be at least about
0.3 moles O2 per hour per total moles of monohydric phenol and polyhydric phenol, or
at least about 0.5 moles O2 per hour per total moles of monohydric phenol and
polyhydric phenol. Also within this range, the oxygen flow may be up to about 2
moles 02 per hour per total moles of monohydric phenol and polyhydric phenol, or up
to about 1 moles O2 per hour per total moles of monohydric phenol and polyhydric
phenol.
[0029] In one embodiment, the copolymerization catalyst may be present in a
concentration such that the catalyst metal ion is present at a concentration of about
0.0001 to about 0.01 moles per total moles of monohydric phenol and polyhydric
phenol. Within this range, the catalyst metal ion concentration may be at least about
0.0002 moles per total moles of monohydric phenol and polyhydric phenol, or at least
about 0.0005 moles per total moles of monohydric phenol and polyhydric phenol.
Also within this range, the catalyst metal ion concentration may be up to about 0.005
moles per total moles of monohydric phenol and polyhydric phenol, or up to about
0.002 moles per total moles of monohydric phenol and polyhydric phenol. The
catalyst amount may also be specified in terms of the weight ratio of total catalyst
components to total monomer. Thus, in one embodiment, the ratio of total moles of
catalyst metal ion, nitrogen-containing ligand, and halide ion to total moles of
monohydric phnol and polyhydric phenol is about 0.005 to about 0.5.
[0030] In one embodiment, the polyfunctional poly(arylene ether) has an
intrinsic viscosity of about 0.04 to about 0.3 deciliter per gram at 25°C in chloroform.
Within this range, the intrinsic viscosity may be at least about 0.06 deciliter per gram,
or at least about 0.09 deciliter per gram. Also within this range, the intrinsic viscosity
may be up to about 0.25 deciliter per gram, or up to about 0.20 deciliter per gram, or
up to about 0.15 deciliter per gram, or up to about 0.12 deciliter per gram.
[0031] The method may be run on any scale, ranging from laboratory scale to
commercial production scale. In one embodiment, method may be run on a batch
scale corresponding to about 70 to about 80,000 pounds of the polyfunctional
poly(arylene ether).
[0032] There is no particular limit on the type of chelating agent used, as long
is it is effective to sequester the catalyst metal ion at the specified concentration. In
one embodiment, the chelating agent is selected from polyalkylenepolyamine
polycarboxylic acids, aminopolycarboxylic acids, aminocarboxylic acids,
polycarboxylic acids, alkali metal salts of the foregoing acids, alkaline earth metal
salts of the foregoing acids, mixed alkali metal-alkaline earth metal salts of the
foregoing acids, and combinations thereof. In one embodiment, the chelating agent is
selected from nitrilotriacetic acid, ethylenediaminetetraacetic acid, alkali metal salts of
the foregoing acids, alkaline earth metal salts of the foregoing acids, mixed alkali
metal-alkaline earth metal salts of the foregoing acids, and mixtures thereof. In one
embodiment, the chelating agent comprises nitrilotriacetic acid or an alkali metal salt
of nitrilotriacetic acid.
[0033] The chelating agent and metal ion are present in a molar ratio of about
1.0 to about 1.5. Within this range, the molar ratio may be at least about 1.05, or at
least about 1.1, or at least about 1.15. Also within this range, the molar ratio may be
up to about 1.4, or up to about 1.3.
[0034] In one embodiment, the polyfunctional poly(arylene ether) solution
may be contacted with the aqueous solution of a chelating agent is conducted at a
temperature of about 30 to about 90°C. Within this range, the temperature may be at
least about 50°C, or at least about 60°C, or at least about 65°C, or at least about 70°C.
Also within this range, the temperature may be up to about 85°C, or up to about 80°C.
[0035] The present inventors have determined that formation of a dispersion
during the chelation step may be minimized if the ratio of the polyfunctional
poly(arylene ether) solution density to the aqueous solution density is maintained at
about 0.6 to about 1.0. Within this range, the ratio may be at least about 0.7, or at
least about 0.9. Another way to minimize dispersion formation is to maintain a
polyfunctional poly(arylene ether) solution viscosity of about 0.5 to about 3,000
centipoise. Within this range, the viscosity may be at least about 5 centipoise, or at
least about 10 centipoise. Also within this range, the viscosity may be up to about
2,000 centipoise, or up to about 500 centipoise. Another way to minimize dispersion
formation is to maintain a ratio of the polyfunctional poly(arylene ether) solution
viscosity to the aqueous solution viscosity of about 0.5 to about 3,000. Within this
range, the ratio may be at least about 5, or at least about 10. Also within this range,
the ratio may be up to about 2,000, or up to about 500.
[0036] Yet another way to minimize dispersion formation is to mix with the
lowest energy during the copolymerization and chelation steps. Thus, in one
embodiment, oxidatively copolymerizing the monohydric phenol and the polyhydric
phenol comprises agitating with a mixing energy of about 10 to about 150 kilojoules
per kilogram total of the monohydric phenol, the polyhydric phenol, the solvent, and
the catalyst. Within this range, the mixing energy may be at least about 30 kilojoules
per kilogram, or at least 50 kilojoules per kilogram. Also within this range, the
mixing energy may be up to about 130 kilojoules per kilogram, or up to 110 kilojoules
per kilogram. In another embodiment, contacting the polyfunctional poly(arylene
ether) solution with the aqueous chelating agent solution comprises agitating the
polyfunctional poly(arylene ether) solution with the aqueous solution with a mixing
energy of about 0.5 to about 25 kilojoules per kilogram total of the polyfunctional
poly(arylene ether) solution and the aqueous solution. Within this range, the mixing
energy may be at least about 1 kilojoule per kilogram, or at least 1.5 kilojoules per
kilogram. Also within this range, the mixing energy may be up to about 20 kilojoules
per kilogram, or up to 15 kilojoules per kilogram.
[0037] While some agitation in the chelation step is necessary to effectively
conduct that step, it is possible to select agitation conditions that minimize dispersion
formation. In one embodiment, contacting the polyfunctional poly(arylene ether)
solution with the aqueous chelating agent solution comprises agitating the
polyfunctional poly(arylene ether) solution with the aqueous solution for about 5 to
about 120 minutes. Within this range, the agitation time may be at least about 15
minutes, or at least about 30 minutes. Also within this range, the agitation time may
be up about 90 minutes, or up to about 60 minutes.
[0038] Chelation and separation can be improved by including a period of
agitation-less contact of the polyfunctional poly(arylene ether) solution and the
aqueous chelating agent solution. Thus, in one embodiment, contacting the
polyfunctional poly(arylene ether) solution with an aqueous solution of a chelating
agent comprises agitating the polyfunctional poly(arylene ether) solution with the
aqueous solution, and subsequently leaving the polyfunctional poly(arylene ether)
solution and the aqueous solution in contact without agitation for about 1 to about 30
hours. Within this range, the period of agitation-less contact may be at least about 4
hours, or at least about 8 hours. Also within this range, the period of agitation-less
contact may be up to about 20 hours.
[0039] Yet other ways to minimize the chance of dispersion formation during
the chelation step include adding solvent to the polyfunctional poly(arylene ether)
solution prior to contacting the polyfunctional poly(arylene ether) solution with the
chelating agent aqueous solution; adding water to the mixture of the polyfunctional
poly(arylene ether) solution and the chelating agent aqueous solution; using a
chelating agent concentration of about 0.01 to about 0.1 weight percent based on the
total weight of the polyfunctional poly(arylene ether) solution and the aqueous
solution of the chelating agent; and using a chelating agent concentration of about 0.5
to about 40 weight percent based on the total weight of the aqueous solution of the
chelating agent. In one embodiment, contacting the polyfunctional poly(arylene ether)
solution with an aqueous solution of a chelating agent comprises using the chelating
agent in an amount of about 0.5 to about 50 weight percent based on the total weight
of the aqueous solution of the chelating agent.
[0040] There is no particular limit on the method used to isolate the
poly(arylene ether) once the chelation step is completed. For example, the
poly(arylene ether) solution and the aqueous chelating agent solution may be
separated with a liquid-liquid centrifuge. Once this separation has been effected, the
polyfunctional pOly(arylene ether) may be isolated from the poiy(arylene ether)
solution using a total isolation method. Suitable total isolation methods include, for
example, devolatilizing extrusion, spray drying, wiped film evaporation, flake
evaporation, and combinations of the foregoing methods. Devolatilizing extrusion is
presently preferred, and the specific techniques of U.S. Patent No. 6,211,327 Bl to
Braat et al. may be employed. The isolated polyfunctional poly(arylene ether) may
have an intrinsic viscosity of about 0.04 to about 0.3 deciliter per gram at 25°C in
chloroform. Within this range, the intrinsic viscosity may be at least about 0.06
deciliter per gram, or at least about 0.09 deciliter per gram. Also within this range, the
intrinsic viscosity may be up to about 0.25 deciliter per gram, or up to about 0.20
deciliter per gram, or up to about 0.15 deciliter per gram, or up to about 0.12 deciliter
per gram.
[0041] Even though it utilizes low levels of chelating agent, the method is
effective to reduce the concentration of catalyst metal in the isolated polyfunctional
poly(arylene ether). Thus, in one embodiment, the isolated polyfunctional
poly(arylene ether) has a concentration of catalyst metal of about 2 to about 5 parts per
million by weight.
[0042] One embodiment is a method of preparing a bifiinctional poly(arylene
ether) resin, comprising: oxidatively copolymerizing a monohydric phenol and an
alkylidenediphenol in an aromatic hydrocarbon solvent in the presence of a catalyst
comprising a metal ion and a nitrogen-containing ligand to form a solution comprising
a bifiinctional poly(arylene ether) having an intrinsic viscosity of about 0.04 to about
0.20 deciliter per gram at 25°C in chloroform; and contacting the bifunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent to extract
the metal ion from the solution; wherein the chelating agent and metal ion are present
in a molar ratio of about 1.0 to about 1.4; wherein the monohydric phenol is selected
from 2,6-dimethylphenol, 2,3,6-trimethylphenol, and mixtures thereof; wherein the
alkylidenediphenol has the structure
(Formula-Removed)

wherein each occurrence of R1 is methyl; each occurrence of R2 is independently
hydrogen or methyl; and each occurrence of R3 is independently hydrogen or methyl;
wherein the aromatic hydrocarbon solvent is selected from benzene, toluene, xylenes,
and combinations thereof; wherein the chelating agent is selected from nitrilotriacetic
acid, ethylenediaminetetraacetic acid, alkali metal salts of the foregoing acids, alkaline

earth metal salts of the foregoing acids, mixed alkali metal-alkaline earth metal salts
of the foregoing acids, and mixtures thereof; and wherein said contacting the
bifunctional poly(arylene ether) solution with an aqueous solution of a chelating agent
is conducted with agitation at about 40 to about 85°C, for about 15 to about 120
minutes, with a mixing energy of about 5 to about 20 kilojoules per kilogram total of
the bifunctional poly(arylene ether) solution and the aqueous solution.
[0043] Another embodiment is a method of preparing a bifunctional
poly(arylene ether) resin, comprising: oxidatively copolymerizing 2,6-dimethyphenol
and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane in toluene in the presence of a
catalyst comprising copper ion and a nitrogen-containing ligand to form a solution
comprising a bifunctional poly(arylene ether) having an intrinsic viscosity of about
0.04 to about 0.15 deciliter per gram at 25°C in chloroform; and contacting the
bifunctional poly(arylene ether) solution with an aqueous solution of nitrilotriacetic
acid trisodium salt to extract the copper ion from the solution; wherein the
nitrilotriacetic acid trisodium salt and copper ion are present in a molar ratio of about
1.1 to about 1.4; wherein the 2,6-dimethyphenol, the 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane, and the toluene are used in amounts such that the ratio of the
total weight of the 2,6-dimethyphenol and the 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane to the total weight of the 2,6-dimethyphenol, the 2,2-bis(3,5-
dimethyl-4-hydroxyphenyl)propane, and the toluene is about 0.26:1 to about 0.34:1;
wherein the nitrogen-containing ligand comprises dibutylamine, dimethylbutylamine,
and N,N'-di-t-butylethylenediamine; wherein said contacting the bifunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent is conducted
with agitation at about 50 to about 80°C, for about 15 to about 120 minutes, with a
mixing energy of about 5 to about 15 kilojoules per kilogram total of the bifunctional
poly(arylene ether) solution and the aqueous solution; wherein said contacting the
bifunctional poly(arylene ether) solution with an aqueous solution of nitrilotriacetic
acid trisodium salt comprises maintaining a ratio of a bifunctional poly(arylene ether)
solution viscosity to an aqueous solution viscosity of about 5 to about 500; and
wherein said contacting the bifunctional poly(arylene ether) solution with an aqueous
solution of nitrilotriacetic acid trisodium salt comprises maintaining a ratio of a
bifunctional poly(arylene ether) solution density to an aqueous solution density of
about 0.8 to about 1.0 gram per milliliter.
[0044] The invention is further illustrated by the following non-limiting
examples.
EXAMPLES 1-4
[0045] Examples 1-4 represent preparations of bifunctional poly(arylene
ether)s having intrinsic viscosities of about 0.12, about 0.09, and about 0.06 deciliter
per gram. These examples also illustrate the effect of chelating agent concentration on
the separation or emulsification of the combined poly(arylene ether) solution and the
aqueous chelating agent solution.
[0046] For each example, a monomer solution was prepared using the
amounts of 2,6-xylenol (2,6-dimethylphenol), 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane ("tetramethylbisphenol A" or "TMBPA"), and toluene
specified in Table 1. The monomer solution was prepared by adding toluene and 2,6-
xylenol to a drum, heating to 60°C, and then adding TMBPA and stirring until all the
TMBPA had dissolved. After the monomer solution was prepared, the reactor was
purged with nitrogen and charged with additional toluene (54.34 kg). The monomer
solution was then added to the reactor, followed by catalyst components dibutylamine
("DBA"), dimethylbutylamine ("DMBA"), a previously blended amine mixture of
N,N'-dibutylethylenediamine ("DBEDA") and didecyl dimethyl ammonium chloride
("PTA") and toluene, and a previously blended mixture of cuprous oxide ("CU2O")
and aqueous hydrogen bromide ("HBr"). At reaction time zero, the oxygen flow rate
was initiated and ramped up to 3.40 standard cubic meters per hour (SCMH) in 0.28
SCMH increments, making sure that the headspace oxygen concentration never
exceeded 13%. After 65 minutes, the reaction mixture was heated so as to attain a
temperature of 49°C at 80 minutes. After the "end of exotherm time" listed in Table
1, the oxygen flow was decreased to maintain a headspace oxygen concentration
below 20%. About 20 to 30 minutes after decreasing the oxygen flow, a sample of the
reaction mixture was removed to analyze intrinsic viscosity, percent solids, hydroxyl
content, residual 2,6-xylenol, and residual TMBPA. The reaction temperature was
increased to 60°C, and the reaction mixture was pumped to a different tank for copper
removal and thermal equilibration. A solution having the Table 1 amount of
trisodium nitrilotriacetate acid ("Na3NTA") in water was prepared and added with
agitation to the reaction mixture, the temperature of which had been increased to
74°C. After two hours, a small sample was removed for visual inspection. The
sample from Example 1 had emulsified. Samples from Examples 2-4 initially had
clearly separated aqueous and organic layers. (For Example 1, additional portions of
Na3NTA solution and toluene were added simultaneously and the mixture was
agitated at 74°C for 15 minutes. For Example 2, additional Na3NTA solution was
added and the mixture was agitated at 74°C remove decimal for 15 minutes. For
Example 4, two additional portions of Na3NTA solution were added, with
emulsification occurring after the third addition of Na3NTA solution; addition of more
toluene resulted in layer separation.) The mixture was then left at 74°C for about 12
hours without any agitation. The dense (aqueous) phase was drawn off, and a small
sample of the light phase was removed for analysis of copper content. All four
examples exhibited copper levels less than 3.5 parts per million. (When the copper
content exceeds 5 parts per million by weight, the NTA addition and equilibration step
may be repeated with 15 minutes agitation and 2 hours without agitation.) The light
(organic, poly(arylene ether)-containing) phase was transferred to a drum.
[0047] Polyfunctional poly(arylene ether) solids were isolated by a total
isolation procedure that consisted of solvent evaporation on a rotary evaporator and
oven drying. The "functionality" (i.e., average number of hydroxyl groups per
poly(arylene ether) chain) was determined by proton nuclear magnetic resonance
spectroscopy ('H NMR).
[0048] These examples demonstrate that the present method is useful for
preparing a low intrinsic viscosity, polyfunctional poly(arylene ether) resin having a
low level of residual catalyst metal while avoiding dispersion formation during
chelation of the catalyst metal.
Table 1
(Table-Removed)
[0049] While the invention has been described with reference to a preferred
embodiment, it will be understood by those skilled in the art that various changes may
be made and equivalents may be substituted for elements thereof without departing
from the scope of the invention. In addition, many modifications may be made to
adapt a particular situation or material to the teachings of the invention without
departing from the essential scope thereof. Therefore, it is intended that the invention
not be limited to the particular embodiment disclosed as the best mode contemplated
for carrying out this invention, but that the invention will include all embodiments
falling within the scope of the appended claims.
[0050] All cited patents, patent applications, and other references are
incorporated herein by reference in their entirety.
[0051] All ranges disclosed herein are inclusive of the endpoints, and the
endpoints are combinable with each other.
[0052] The use of the terms "a" and "an" and "the" and similar referents in the
context of describing the invention (especially in the context of the following claims)
are to be construed to cover both the singular and the plural, unless otherwise
indicated herein or clearly contradicted by context. Further, it should further be noted
that the terms "first," "second," and the like herein do not denote any order, quantity,
or importance, but rather are used to distinguish one element from another. The
modifier "about" used in connection with a quantity is inclusive of the stated value
and has the meaning dictated by the context (e.g., it includes the degree of error
associated with measurement of the particular quantity).

CLAIMS:
1. A method of preparing a poly(arylene ether) resin, comprising:
oxidatively copolymerizing a monohydric phenol and a polyhydric phenol in
an aromatic hydrocarbon solvent in the presence of a catalyst comprising a metal ion
and a nitrogen-containing ligand to form a solution comprising a polyfunctional
poly(arylene ether) having an intrinsic viscosity of about 0.04 to about 0.3 deciliter per
gram at 25°C in chloroform; and
contacting the polyfunctional poly(arylene ether) solution with an aqueous
solution of a chelating agent to extract the metal ion from the solution; wherein the
chelating agent and metal ion are present in a molar ratio of about 1.0 to about 1.5.
2. The method of claim 1, wherein the monohydric phenol has the
structure

(Formula-Removed)
wherein each occurrence of Q1 is independently halogen, primary or secondary C1-C12
alkyl, C2-C12 alkenyl, C3-C12 alkenylalkyl, C3-C12 alkynyl, C3-C12 alkynylalkyl, C1-C12
aminoalkyl, C1-C12 hydroxyalkyl, C6-C12 aryl, C1-C12 haloalkyl, C1-C12
hydrocarbonoxy, C1-C12 halohydrocarbonoxy wherein at least two carbon atoms
separate the halogen and oxygen atoms; and wherein each occurrence of Q2 is
independently hydrogen, halogen, primary or secondary C1-C12 alkyl, C1-C12 alkenyl,
C3-C12 alkenylalkyl, C2-C12 alkynyl, C3-C12 alkynylalkyl, C1-C12 aminoalkyl, C1-C12
hydroxyalkyl, C6-C12 aryl, C1-C12 haloalkyl, C1-C12 hydrocarbonoxy, C1-C12
halohydrocarbonoxy wherein at least two carbon atoms separate the halogen and
oxygen atoms.
3. The method of claim 1, wherein the monohydric phenol is selected
from 2,6-dimethylphenol, 2,3,6-trimethylphenol, and mixtures thereof.
4. The method of claim 1, wherein the polyhydric phenol comprises 2 to
about 8 phenolic hydroxy groups.
5. The method of claim 1, wherein the polyhydric phenol is a dihydric
phenol having the structure
(Formula-Removed)
wherein each occurrence of R1 and R2 is independently hydrogen, halogen, primary or
secondary C1-C12 alkyl, C1-C12 alkenyl, C1-C12 alkynyl, C1-C12 aminoalkyl, C1-C12
hydroxyalkyl, C6-C12 aryl (including phenyl), C1-C12 haloalkyl, C1-C12
hydrocarbonoxy, C1-C12 halohydrocarbonoxy wherein at least two carbon atoms
separate the halogen and oxygen atoms; Z is 0 or 1; and Y is selected from
(Formula-Removed)
wherein each occurrence of R3-R6 is independently hydrogen or C1-C12 hydrocarbyl.
6. The method of claim 5, wherein each occurrence of R1 is methyl, each
occurrence of R2 and R3 is independently hydrogen or methyl.
7. The method of claim 1, wherein the polyhydric phenol is selected from
l,l-bis(3,5-dimethyl-4-hydroxyphenyl)ethane, l,l-bis(3-chloro-4-
hydroxyphenyl)ethane, 1,1 -bis(3-methyl-4-hydroxyphenyl)-ethane, 1,2-bis(4-hydroxy-
3,5-dimethylphenyl)-l,2-diphenylethane, l,2-bis(3-methyl-4-hydroxyphenyl)-l,2-
diphenylethane, l,2-bis(3-methyl-4-hydroxyphenyl)ethane, 2,2'-binaphthol,
2,2'biphenol, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4-
methoxybenzophenone, 2,2'-dihydroxybenzophenone, 2,2-bis(3,5-dichloro-4-
hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3-
phenyl-4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-
bis(3,5-dimethyl-4-hydroxyphenyl)propane, l,l-bis(3,5-dimethyl-4-hydroxyphenyl)-l-
phenylethane, 1,1-bis(3-chloro-4-hydroxyphenyl)-1-phenylethane, 1,l-bis(3-methyl-4-
hydroxyphenyl)-l-phenylethane, 2,2-bis(4-hydroxy-3,5-dimethyl phenyl)-l-
phenylpropane, 2,2-bis(4-hydroxy-3,5-dimethyl phenyl)hexane, 2,2-bis(4-hydroxy-
3,5-dimethylphenyl)pentane, 2,2-bis(3-methyl-4-hydroxynaphthyl)propane, 2,2-bis(3-
methyl-4-hydroxyphenyl)-1 -phenylpropane, 2 2-bis(3-methyl-4-
hydroxyphenyl)hexane, 2,2-bis(3-methyl-4-hydroxyphenyl)pentane, 2,2'-
methylenebis(4-methylphenol), 2,2'-methylenebis[4-methy l-6-( 1 -
methylcyclohexyl)phenol], 3,3',5,5'-tetramethyl-4,4'-biphenol, 3,3'-dimethyl-4,4'-
biphenol, bis(2-hydroxyphenyl)-methane, bis(4-hydroxy-2,6-dimethyl-3-
methoxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-
hydroxyphenyl)methane, bis-(4-hydroxy-3,5-dimethyl phenyl)-cyclohexylmethane,
bis(4-hydroxy-3,5-dimethyl phenyl)phenylmethane, bis(3-methyl-4-
hydroxyphenyl)cyclohexylmethane, bis(3-methyl-4-hydroxyphenyl)methane, bis(3,5-
dimethyl-4-hydroxyphenyl)methane, bis(3-methyl-4-hydroxyphenyl)phenylmethane,
2,2',3,3',5,5'-hexamethyl-4,4'-biphenol, octafluoro-4,4'-biphenol, 2,3,3',5,5'-
pentamethyl-4,4'-biphenol, 1,1-bls(3,5-dibromo-4-hydroxyphenyl)cyclohexane 1,1-
bis(3,5 -dimethyl-4-hydroxyphenyl)cyclohexane, bis(3 -methyl-4-
hydroxyphenyl)cyclohexane, tetrabromobiphenol, tetrabromobisphenol A,
tetrabromobisphenol S, 2,2'-diallyl-4,4'-bisphenol A, 2,2'-diallyl-4,4'-bisphenol S,
3,3',5,5'-tetramethyl-4,4'-bisphenol sulfide, 3,3'-dimethyl bisphenol sulfide,
3,3',5,5'-tetramethyl-4,4'-bisphenol sulfone and combinations thereof.
8. The method of claim 1, wherein the polyhydric phenol comprises 2,2-
bis(3,5 -dimethyl-4-hydroxyphenyl)propane.
9. The method of claim 1, wherein the polyhydric phenol comprises 3 or
4 phenolic hydroxy groups.
10. The method of claim 9, wherein the polyhydric phenol is selected from
1,1,1 -tris(3,5-dimethyl-4-hydrxyphenyl)ethane 1,1,1 -tris(3-methyl-4-
hydroxyphenyl)ethane, l,3,5-tris(3,5-dimethyl-4-hydroxyphenyl-l -keto)benzene,
l,3,5-tris(3,5-dimethyl-4hydroxyphenyl-l-isopropylidene)benzene, 2,2,4,4-tetrakis(3-
methyl-4hydroxyphenyl)pentane, 2,2,4,4-tetrakis(3,5-dimethyl-4-
hydroxyphenyl)pentane, 1,1,4,4-tetrakis(3-methyl-4-hydroxyphenyl)cyclohexane,
1,1,4,4-tetrakis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,3,5-tris(3,5-dimethyl-4-
hydroxyphenyl)benzene, 1,3,5-tris(3-methyl-4-hydroxyphenyl)benzene, 2,6-bis(2-
hydroxy-5-methylbenzyl)-4-methyl phenol, 4,6-dimethyl-2,4,6-tris(4-hydroxy-3-
methylphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxy-3,5-dimethylphenyl)-2-
heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxy-3-methylphenyl)heptane, 4,6-dimethyl-
2,4,6-tris(4-hydroxy-3-methylphenyl)heptane, 2,4-bis(4-hydroxy-3-
methylphenylisopropyl)phenol, 2,4-bis(4-hydroxy-3,5-
dimethylphenylisopropyl)phenol, tetrakis(4-hydroxy-3-methylphenyl)methane,
tetrakis(4-hydroxy-3,5-dimethylphenyl)methane, tetrakis(4-[4-hydroxy-3-
methylphenylisopropyl]-phenoxy)methane, tetrakis(4-[4-hydroxy-3,5-
dimethylphenylisopropyl]-phenoxy)methane, and combinations thereof.
11. The method of claim 1, wherein the polyhydric phenol comprises a
dihydric phenol and a polyhydric phenol comprising 3 to 8 phenolic hydroxy groups.

12. The method of claim 1, wherein the monohydric phenol and the
polyhydric phenol are copolymerized in a mole ratio of about 3 to about 110.
13. The method of claim 1, wherein the aromatic hydrocarbon solvent is
selected from benzene, toluene, xylenes, and combinations thereof.
14. The method of claim 1, wherein the aromatic hydrocarbon solvent
comprises toluene.
15. The method of claim 1, wherein the solvent further comprises a C3-C8
aliphatic alcohol.
16. The method of claim 14, wherein the solvent fuither comprises
ethanol, methanol, or a combination thereof.
17. The method of claim 1, wherein the monohydric phenol, the polyhydric
phenol, and the solvent are used in amounts such that a ratio of the total weight of the
monohydric phenol and the polyhydric phenol to the total weight of the monohydric
phenol, the polyhydric phenol, and the solvent is about 0.1:1 to about 0.5:1.
18. The method of claim 1, wherein the metal ion is selected from ions of
copper, manganese, cobalt, iron, and combinations thereof.
19. The method of claim 1, wherein the metal ion comprises copper ion.
20. The method of claim 1, wherein the nitrogen-containing ligand is
selected from alkylenediamine ligands, primary monoamines, secondary monoamines,
tertiary monoamines, aminoalcohols, oximes, oxines, cyanide, and combinations
thereof.

21. The method of claim 1, wherein the nitrogen-containing ligand is
selected from dibutylamine, dimethylbutylamine, N,N'-di-t-butylethylenediamine,
pyridine, and combinations thereof.
22. The method of claim 1, wherein the nitrogen-containing ligand
comprises dibutylamine, dimethylbutylamine, and N,N'-di-t-butylethylenediamine.
23. The method of claim 1, wherein said oxidatively copolymerizing a
monohydric phenol and a polyhydric phenol comprises adding all of the monohydric
phenol and all of the polyhydric phenol to the reactor before initiating polymerization.
24. The method of claim 1, wherein said oxidatively copolymerizing a
monohydric phenol and a polyhydric phenol comprises adding all of the polyhydric
phenol to the reactor before initiating polymerization, and adding an amount of the
monohydric phenol before initiating polymerization such that a molar ratio of
monohydric phenol to polyhydric phenol is about 0.1 to about 30 before initiating
polymerization.
25. The method of claim 1, wherein said oxidatively copolymerizing a
monohydric phenol and a polyhydric phenol comprises adding an amount of the
polyhydric phenol and an amount of the monohydric phenol and an amount of the
solvent to the reactor before initiating polymerization, such that a ratio of the total of
the amount of the polyhydric phenol and the amount of the monohydric phenol to the
total of the amount of the polyhydric phenol and the amount of the monohydric phenol
and the amount of the solvent is about 0.1:1 to about 0.5:1.
26. The method of claim 1, wherein said oxidatively copolymerizing a
monohydric phenol and a polyhydric phenol comprises maintaining a reaction
temperature of about 20 to about 80°C.
27. The method of claim 1, wherein said oxidatively copolymerizing a
monohydric phenol and a polyhydric phenol comprises maintaining an oxygen flow
rate of about 0.1 to about 3 moles O2 per hour per total moles of monohydric phenol
and polyhydric phenol.
28. The method of claim 1, wherein said oxidatively copolymerizing a
monohydric phenol and a polyhydric phenol is conducted over the course of about 0.5
to about 5 hours.
29. The method of claim 1, wherein said oxidateively copolymerizing a
monohydric phenol and polyhydric phenol comprises using a catalyst metal ion
concentration of about 0.0001 to about 0.01 mole per total moles of monohydric
phenol and polyhydric phenol.
30. The method of claim 1, wherein said catalyst further comprises a halide
ion, and wherein a ratio of total moles of metal ion, nitrogen-containing ligand, and
halide ion to total moles of monohydric phenol and polyhydric phenol is about 0.005
to about 0.5.
31. The method of claim 1, wherein the polyfunctional poly(aryiene ether)
has an intrinsic viscosity of about 0.04 to about 0.15 deciliter per gram at 25°C in
chloroform.
32. The method of claim 1, wherein the chelating agent is selected from
polyalkylenepolyamine polycarboxylic acids, aminopolycarboxylic acids,
aminocarboxylic acids, polycarboxylic acids, alkali metal salts of the foregoing acids,
alkaline earth metal salts of the foregoing acids, mixed alkali metal-alkaline earth
metal salts of the foregoing acids, and combinations thereof.
33. The method of claim 1, wherein the chelating agent is selected from
nitrilotriacetic acid, ethylenediaminetetraacetic acid, alkali metal salts of the foregoing
acids, alkaline earth metal salts of the foregoing acids, mixed alkali metal-alkaline
earth metal salts of the foregoing acids, and mixtures thereof.
34. The method of claim 1, wherein the chelating agent comprises
nitrilotriacetic acid or an alkali metal salt of nitrilotriacetic acid.
35. The method of claim 1, wherein the chelating agent and metal ion are
present in a molar ratio of about 1.1 to about 1.4.
36. The method of claim 1, wherein the chelating agent and metal ion are
present in a molar ratio of about 1.1 to about 1.3.
37. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent is conducted
at a temperature of about 30 to about 90°C.
38. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent comprises
maintaining a ratio of a polyfunctional poly(arylene ether) solution density to an
aqueous solution density of about 0.6 to about 1.0.
39. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent comprises
maintaining a polyfunctional poly(arylene ether) solution viscosity of about 0.5 to
about 3,000 centipoise.
40. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent comprises
maintaining a ratio of a polyfunctional poly(arylene ether) solution viscosity to an
aqueous solution viscosity of about 0.5 to about 3,000.
41. The method of claim 1, wherein said oxidatively copolymerizing a
monohydric phenol and a polyhydric phenol comprises agitating with a mixing energy
of about 10 to about 150 kilojoules per kilogram total of the monohydric phenol, the
polyhydric phenol, the solvent, and the catalyst.
42. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent comprises
agitating the polyfunctional poly(arylene ether) solution with the aqueous solution
with a mixing energy of about 0.5 to about 25 kilojoules per kilogram total of the
polyfunctional poly(arylene ether) solution and the aqueous solution.
43. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent comprises
agitating the polyfunctional poly(arylene ether) solution with the aqueous solution for
about 5 to about 120 minutes.
44. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent comprises
agitating the polyfunctional poly(arylene ether) solution with the aqueous solution,
and subsequently leaving the polyfunctional poly(arylene ether) solution and the
aqueous solution in contact without agitation for about 1 to about 30 hours.
45. The method of claim 1, further comprising adding solvent to the
polyfunctional poly(arylene ether) solution prior to said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent.
46. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent further
comprises contacting the polyfunctional poly(arylene ether) solution and the aqueous
solution with additional water.
47. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent comprises
using the chelating agent in an amount of about 0.01 to about 0.1 weight percent based
on the total weight of polyfunctional poly(arylene ether) solution and the aqueous
solution of the chelating agent.
48. The method of claim 1, wherein said contacting the polyfunctional
poly(arylene ether) solution with an aqueous solution of a chelating agent comprises
using the chelating agent in an amount of about 0.5 to about 50 weight percent based
on the total weight of the aqueous solution of the chelating agent
49. The method of claim 1, further comprising isolating the polyfunctional
poly(arylene ether), wherein the isolated polyfunctional poly(arylene ether) has a
concentration of catalyst metal of about 2 to about 5 parts per million by weight.
50. A method of preparing a poly(arylene ether) resin, comprising:
oxidatively copolymerizing a monohydric phenol and an alkylidenediphenol in
an aromatic hydrocarbon solvent in the presence of a catalyst comprising a metal ion
and a nitrogen-containing ligand to form a solution comprising a bifunctional
poly(arylene ether) having an intrinsic viscosity of about 0.04 to about 0.20 deciliter
per gram at 25°C in chloroform; and
contacting the bifunctional poly(arylene ether) solution with an aqueous
solution of a chelating agent to extract the metal ion from the solution; wherein the
chelating agent and metal ion are present in a molar ratio of about 1.0 to about 1.4;
wherein the monohydric phenol is selected from 2,6-dimethylphenol, 2,3,6-
trimethylphenol, and mixtures thereof;
wherein the alkylidenediphenol has the structure
(Formula Removed)
]wherein each occurrence of R1 is methyl; each occurrence of R2 is independently hydrogen or methyl; and each occurrence of R3 is independently hydrogen or methyl;
wherein the aromatic hydrocarbon solvent is selected from benzene, toluene, xylenes, and combinations thereof;
wherein the chelating agent is selected from nitrilotriacetic acid, ethylenediaminetetraacetic acid, alkali metal salts of the foregoing acids, alkaline earth metal salts of the foregoing acids, mixed alkali metal-alkaline earth metal salts of the foregoing acids, and mixtures thereof; and
wherein said contacting the bifunctional poly(arylene ether) solution with an aqueous solution of a chelating agent is conducted with agitation at about 40 to about 85°C, for about 15 to about 120 minutes, with a mixing energy of about 5 to about 20 kilojoules per kilogram total of the bifunctional poly(arylene ether) solution and the aqueous solution.
51. A method of preparing a poly(arylene ether) resin, comprising:
oxidatively copolymerizing 2,6-dimethyphenol and 2„2-bis(3.5-dimethyl-4-hydroxyphenyl)propane in toluene in the presence of a catalyst comprising copper ion and a nitrogen-containing ligand to form a solution comprising a bilunctional poly(arylene ether) having an intrinsic viscosity of about 0.04 to about 0.15 deciliter per gram at 25°C in chloroform; and
contacting the bifunctional poly(arylene ether) solution with an aqueous solution of nitrilotriacetic acid trisodium salt to extract the copper ion from the

solution; wherein the nitrilotriacetic acid trisodium salt and copper ion are present in a
molar ratio of about 1.1 to about 1.4;
wherein the 2,6-dimethyphenol, the 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane, and the toluene are used in amounts such that the ratio of the
total weight of the 2,6-dimethyphenol and the 2,2-bis(3,5-dimethyl-4-
hydroxyphenyl)propane to the total weight of the 2,6-dimethyphenol, the 2,2-bis(3,5-
dimethyl-4-hydroxyphenyl)propane, and the toluene is about 0.26:1 to about 0.34:1;
wherein the nitrogen-containing ligand comprises dibutylamine,
dimethylbutylamine, and N,N'-di-t-butylethylenediamine;
wherein said contacting the bifunctional poly(arylene ether) solution with an
aqueous solution of a chelating agent is conducted with agitation at about 50 to about
80°C, for about 15 to about 120 minutes, with a mixing energy of about 5 to about 15
kilojoules per kilogram total of the bifunctional' poly(arylene ether) solution and the
aqueous solution;
wherein said contacting the bifunctional poly(arylene ether) solution with an
aqueous solution of nitrilotriacetic acid trisodium salt comprises maintaining a ratio of
a bifunctional poly(arylene ether) solution viscosity to an aqueous solution viscosity
of about 5 to about 500; and
wherein said contacting the bifunctional poly(arylene ether) solution with an
aqueous solution of nitrilotriacetic acid trisodium salt comprises maintaining a ratio of
a bifunctional poly(arylene ether) solution density to an aqueous solution density of
about 0.8 to about 1.0.