U.S. patent application number 16/687765 was filed with the patent office on 2020-03-19 for methods of making stable and thermally polymerizable vinyl, amino or oligomeric phenoxy benzocyclobutene monomers with improvied.
The applicant listed for this patent is Rohm and Haas Electronic Materials LLC. Invention is credited to Michael K. Gallagher, Colin Hayes, Michelle Riener.
Application Number | 20200087429 16/687765 |
Document ID | / |
Family ID | 64901287 |
Filed Date | 2020-03-19 |
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United States Patent
Application |
20200087429 |
Kind Code |
A1 |
Hayes; Colin ; et
al. |
March 19, 2020 |
METHODS OF MAKING STABLE AND THERMALLY POLYMERIZABLE VINYL, AMINO
OR OLIGOMERIC PHENOXY BENZOCYCLOBUTENE MONOMERS WITH IMPROVIED
CURING KINETICS
Abstract
The present invention provides methods of making low energy
polymerizable monomers and resins for use in making dielectric
materials. The methods comprise deprotecting or deacylating an
organic alkali cleavable protecting group containing addition
polymerizable, amine containing aromatic monomer or oligoaromatic
phenol resin containing an organic alkali cleavable protecting
group, such as a C.sub.2 to C.sub.9 alkanoyl group, preferably, an
acyl group, by hydrolyzing to remove the protecting group in
organic alkali in a polar solvent containing an excess of alkali
C.sub.1 to C.sub.7 alkoxide and form a hydroxyl functional monomer
or resin, followed by; reacting via nucleophilic substitution the
resulting hydroxyl functional monomer or resin with an alpha-halide
(a-halide) or strong acid conjugate leaving group containing
arylcyclobutene compound in a polar solvent, to yield a product an
arylcyclobutene-containing addition polymerizable or amine
containing aromatic monomer or oligoaromatic phenol resin having an
ether linkage from the cyclobutene ring to an aromatic group of the
addition polymerizable aromatic monomer, aromatic amine or
oligoaromatic phenol.
Inventors: |
Hayes; Colin; (Marlborough,
MA) ; Gallagher; Michael K.; (Hopkinton, MA) ;
Riener; Michelle; (Watertown, MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Rohm and Haas Electronic Materials LLC |
Marlborough |
MA |
US |
|
|
Family ID: |
64901287 |
Appl. No.: |
16/687765 |
Filed: |
November 19, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
15828972 |
Dec 1, 2017 |
10513568 |
|
|
16687765 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C07C 35/31 20130101;
C08F 32/02 20130101; C08G 81/025 20130101; C08F 212/08 20130101;
C07C 69/017 20130101; C07C 23/18 20130101; C08F 12/22 20130101;
C08K 5/09 20130101; C08F 12/02 20130101; G01N 25/4866 20130101;
C07C 41/01 20130101; C08F 212/08 20130101; C08F 212/32 20130101;
C08F 212/08 20130101; C08F 212/14 20130101; C07C 41/01 20130101;
C07C 43/243 20130101; C08F 212/08 20130101; C08F 212/22
20200201 |
International
Class: |
C08F 32/02 20060101
C08F032/02; C08F 212/08 20060101 C08F212/08; C08F 12/22 20060101
C08F012/22; C07C 41/01 20060101 C07C041/01; C08F 12/02 20060101
C08F012/02; C08G 81/02 20060101 C08G081/02; C07C 69/017 20060101
C07C069/017; C07C 35/31 20060101 C07C035/31; C07C 23/18 20060101
C07C023/18; C08K 5/09 20060101 C08K005/09 |
Claims
1. A benzocyclobutene compound selected from the group consisting
of: 4-vinyl phenoxy benzocyclobutene, 4-amino phenoxy
benzocyclobutene, ##STR00016##
2. The benzocyclobutene compound of claim 1, wherein the vinyl
benzocyclobutene compound selected from the group consisting of:
4-amino phenoxy benzocyclobutene, ##STR00017##
3. A monomer having the structure ##STR00018## wherein K is a
divalent group chosen from a divalent aryloxy group having from 1
to 10 aryl or phenol rings, or an oligophenolic group having from 1
to 10 phenol units; M is a divalent aromatic group chosen from a
C.sub.1 to C.sub.6 alkyl substituted or unsubstituted aromatic
radical group or a C.sub.1 to C.sub.6 alkyl substituted or
unsubstituted divalent heteroaromatic radical group; L.sub.1 is a
covalent bond; and R.sub.1 through R.sub.6 are each independently
selected from a monovalent group chosen from hydrogen, deuterium,
halide, hydroxyl, a C.sub.1 to C.sub.6 alkyl group, a C.sub.1 to
C.sub.6 alkoxy group, a C.sub.1 to C.sub.6 alkyl substituted
hydrocarbon group, a heteroatom containing hydrocarbon group, a
C.sub.1 to C.sub.6 alkyl substituted heterohydrocarbon group, a
cyano group, or an hydroxyl group.
5. The monomer of claim 4 wherein each of R.sub.1, R.sub.2 and
R.sub.3 is hydrogen.
6. The monomer of claim 4 wherein each of R.sub.1 through R.sub.6
is hydrogen.
Description
[0001] This application is a continuation of U.S. application Ser.
No. 15/828,92, filed on Dec. 1, 2017, now allowed.
[0002] The present invention relates generally to methods of making
monomer materials, and, more particularly, to methods of making
addition polymerizable, aromatic amine or oligoaromatic phenol
arylcyclobutene-containing monomers or resins having one or more
aryloxy, such as phenoxy, or oligophenolic groups comprising
reacting an alpha-halide (a-halide) or strong acid conjugate
leaving group, such as a sulfonate leaving group, for example, an
o-tosyl or triflate leaving group, containing arylcyclobutene
compound, such as a 1-bromobenzocyclobutene (a-Br BCB), with an
hydroxyl functional aromatic monomer or oligoaromatic resin
containing an addition polymerizable group, containing an amine
group, or an oligoaromatic resin containing one or more phenol ring
or phenolic hydroxyl group. The hydroxyl functional aromatic
monomer or oligoaromatic resin is formed by deprotecting it in
organic alkali and a polar solvent to remove an organic alkali
cleavable protecting group from a protecting group containing
aromatic monomer or oligoaromatic resin.
[0003] Vinyl benzocyclobutene (vinyl BCB) styrenic copolymers
provide many of the dielectric benefits known BCB containing
dielectrics at a significantly reduced cost. However, unsubstituted
BCB monomers require a 250.degree. C. temperature for 1 hour for
cure, which renders them unsuitable for use with many polymer or
plastic materials. Substitution of the BCB ring can afford reduced
cure temperatures, but often requires several additional synthetic
steps and often results in low monomer yields (<70%) in unstable
monomer compounds. For example, known alkoxy substituted BCBs do
not survive thermal radical polymerizations due to ring opening
polymerization of the BCB and so are unsuitable for applications
which require orthogonal cure among addition and ring opening.
[0004] Previously, Harth et al. in "Synthesis of low-temperature
cross-linker and utilization," Polymer Chemistry, 2012, 3(4), at
857-860, teach a 1-substituted alkoxy BCB having the alkoxy group
on the cyclobutene ring, which is grafted to a poly(acrylic acid)
post-polymerization to impart a low temperature cure property for
the BCB groups. Recent experiments produced a 1-alkoxy methacrylate
BCB and isolated the monomer through use of an expensive silver
catalyst; however, the material was unstable at 80.degree. C. where
conventional free radical polymerizations are carried out leading
to a styrenic polymer that is highly crosslinked and not further
curable through a Diels Alder cycloaddition.
[0005] Further, aliphatic alkoxy BCBs are thermally processed at
too low a temperature for many applications, such as spin coating
on a wafer and subsequent removal of the solvent owing to the high
boiling point of solvents required for safe operation in
semiconductor fabrication. Such aliphatic alkoxy linkages are known
to lower ring opening thereby disabling the orthogonal Diels Alder
reaction.
[0006] The present inventors have sought to solve the problem of
providing a simple method for making a stable addition
polymerizable BCB monomer useful for making a dielectric material
that enables the provision of addition polymerized and ring opening
cured (co)polybenzocyclobutenes having a low dielectric constant
and low dielectric loss.
STATEMENT OF THE INVENTION
[0007] In accordance with a first aspect of the present invention,
a method of making a monomer or resin composition comprises
deprotecting or deacylating an addition polymerizable or amine
containing aromatic monomer or an oligoaromatic resin containing an
organic alkali cleavable protecting group, such as a C.sub.2 to
C.sub.9 alkanoyl group, preferably, an acyl group; or an alkyl
carbonate group, such as methyl carbonate, preferably, the monomer
or resin being an addition polymerizable group containing monomer,
or, more preferably, an acetoxystyrene, by hydrolyzing to remove
the organic alkali cleavable protecting group in organic alkali and
a polar solvent containing an excess of alkali C.sub.1 to C.sub.7
alkoxide, preferably, alkali C.sub.1 to C.sub.4 alkoxide or, more
preferably, sodium methoxide to form an hydroxyl functional
addition polymerizable aromatic monomer, such as 4-vinyl phenol or
4-vinyl napthol; a hydroxyl functional aromatic amine containing
monomer, for example, 4-aminophenol; or an oligoaromatic phenol
compound containing one or more phenolic hydroxyl, such as a
phenolic novolac or resole; preferably, a hydroxystyrene, followed
by; reacting via nucleophilic substitution the resulting hydroxyl
functional addition polymerizable aromatic monomer, hydroxyl
functional aromatic amine functional group containing monomer or
hydroxyl functional oligoaromatic compound with an alpha-halide
(a-halide) or strong acid conjugate leaving group containing
arylcyclobutene compound, preferably, having a bromide, on the
cyclobutene ring, or, more preferably, a 1-bromobenzocyclobutene
(a-Br BCB), in a polar solvent, such as a polar protic solvent,
such as an alkanol or alkanone, or polar aprotic solvent, such as
an ether, an alkyl ester or amide, preferably, a non-aqueous
solvent or anhydrous solvent, to yield a product
arylcyclobutene-containing addition polymerizable monomer, aromatic
amine functional group monomer or oligoaromatic phenol having an
ether linkage from the cyclobutene ring to an aromatic group of the
addition polymerizable aromatic monomer, aromatic amine or
oligoaromatic phenol, preferably, an oligoaromatic phenol resin
containing from one to six, more preferably, from two to four,
arylcyclobutene groups.
[0008] In accordance with the methods of making a monomer or resin
composition of the first aspect of the present invention, the
reacting via nucleophilic substitution comprises heating the
hydroxyl functional addition polymerizable aromatic monomer,
hydroxyl functional aromatic amine containing monomer or hydroxyl
functional oligaromatic compound with the alpha-halide (a-halide)
or strong acid conjugate leaving group containing arylcyclobutene
compound in an organic alkali and polar solvent to from 55 to
80.degree. C., or, preferably, from 60 to 75.degree. C.,
preferably, in the presence of a free radical inhibitor.
[0009] In accordance with methods of making a monomer or resin
composition of the first aspect of the present invention, the
hydroxyl functional addition polymerizable aromatic monomer,
hydroxyl functional aromatic amine containing monomer or hydroxyl
functional oligoaromatic compound formed by deprotecting or
deacylating comprises a hydroxyl functional addition polymerizable
aromatic monomer chosen from a styrene alcohol; a vinylphenol; an
allyl phenol; an alkynyl phenol; a vinyl naphthol; a vinyl
oligophenol; a vinylphenol having multiple vinyl groups,
preferably, 2 to 6 vinyl groups; a vinylphenol having multiple
vinyl groups and multiple aromatic rings, such as from 2 to 20
aromatic rings, or, preferably, from 2 to 6 of each of vinyl groups
and aromatic rings; an allyloligophenol having from 2 to 20, or,
preferably, from 2 to 6 aromatic rings or phenolic rings; an
alkynyloligophenol having from 2 to 20, or, preferably, from 2 to 6
aromatic rings or phenolic rings.
[0010] In accordance with the methods of making a monomer or resin
composition of the first aspect of the present invention, wherein
when the hydroxyl functional addition polymerizable aromatic
monomer, hydroxyl functional aromatic amine or hydroxyl functional
oligoaromatic phenol formed by deprotecting or deacylating
comprises a vinyl oligophenol having from 2 to 10 aromatic rings or
phenolic rings, an aminophenol, an amino oligophenol or any
oligoaromatic phenol, it is substantially free of aldehydes.
[0011] Preferably, the hydroxyl functional addition polymerizable
aromatic monomer, hydroxyl functional aromatic amine containing
monomer or hydroxyl functional oligoaromatic compound formed by
deprotecting or deacylating comprises a compound of any of the
formulae (1) to (9) or (D), below:
##STR00001## ##STR00002##
wherein R is independently any of H, CH.sub.3, CH.sub.3CH.sub.2--,
--C(CH.sub.3).sub.2--, --C(CH.sub.3)(CH.sub.2CH.sub.3)--,
--C(Ph.sub.2))--, SO.sub.2 or Ph-, wherein Ph is phenyl; and
wherein n is an integer of from 0 to 10; and, further wherein, when
the hydroxyl functional monomer or resin is a hydroxyl functional
aromatic amine containing monomer, at least one aromatic ring
contains an amine group.
[0012] In accordance with methods of making a monomer or resin
composition of the first aspect of the present invention, wherein
the organic alkali cleavable protecting group on the protecting
group containing aromatic monomer or oligoaromatic resin is chosen
from a C.sub.2 to C.sub.9 alkanoyl group, such as acyl, alkyl
substituted acyl, propionyl, butyryl, pivaloyl, alkylpivaloyl, a
halogenated acyl group, such as a trifluoro acyl group (other), a
benzoate or an alkyl benzoate; or an alkyl carbonate, such as a
methyl carbonate or a 9-fluoreneylmethyl carbonate (FMoc);
preferably, a C.sub.2 to C.sub.7 alkanoyl group, or, more
preferably, an acyl or alkyl substituted acyl group.
[0013] In accordance with methods of making a monomer or resin
composition of the first aspect of the present invention, the
protecting group containing aromatic monomer or oligoaromatic resin
having an organic alkali cleavable protecting group can be a
compound of any of the formulae A1 or A2, below, wherein Ac
represents an acyl or alkyl substituted acyl, and R represents any
of a C.sub.1 to C.sub.6 divalent aliphatic hydrocarbon radical,
e.g. alkylene, such as methylene, secondary and tertiary alkylenes,
for example, isobutylene or tert-butylene or halogenated branched
alkylenes, such as ditrifluoromethyl-substituted alkylenes; or an
ether containing divalent hydrocarbon:
##STR00003##
[0014] In accordance with methods of making a monomer or resin
composition of the first aspect of the present invention, the
methods further comprise purifying the product
arylcyclobutene-containing addition polymerizable monomer, aromatic
amine containing monomer or oligoaromatic phenol resin having an
ether linkage from the cyclobutene ring to an aromatic group of the
addition polymerizable aromatic monomer, aromatic amine or
oligoaromatic phenol, such as by extracting the monomer in an
aqueous polar solvent mixture, such as water and ethyl acetate,
preferably, followed by removing the aqueous component by
extracting it with a base, an alkali metal halide salt, or both,
combining the organic residues from the monomer extract and the
aqueous extraction, and then drying the combined organic
residues.
[0015] In accordance with methods of making a monomer or resin
composition of the first aspect of the present invention, the
methods further comprise reacting the product
arylcyclobutene-containing aromatic amine having an ether linkage
from the cyclobutene ring to an aromatic group of the aromatic
amine with an unsaturated anyhydride, preferably, maleic anhydride,
in the presence of a radical inhibitor to form an aromatic
maleimide of an arylcyclobutene-containing aromatic maleimide
monomer having an ether linkage from the cyclobutene ring to an
aromatic group of the maleimide. Alternatively, other unsaturated
anhydrides can be used to generate polymerizable imides such as,
itaconic anhydride, 4-ethynyl phthallic anhydride, 4-methylethynyl
phthallic anhydride, and 4-phenyl ethynyl phthallic anhydride.
[0016] In accordance with a second aspect of the present invention,
monomer or resin compositions comprise one or more
arylcyclobutene-containing, such as a benzocyclobutene
(BCB)-containing, addition polymerizable monomer, aromatic amine or
oligoaromatic phenol monomer or resin having an ether linkage from
the cyclobutene ring to an aromatic group of the addition
polymerizable aromatic monomer, aromatic amine or oligoaromatic
phenol in a purity of at least 90 wt, %, or, preferably, at least
95 wt. % of the composition, preferably, as a solid.
[0017] In accordance with the monomer or resin compositions of the
second aspect of the present invention, wherein the monomer is
substantially free of 2-methylbenzaldehyde, as in the following
formula V:
##STR00004##
[0018] In accordance with the monomer or resin compositions of the
second aspect of the present invention, wherein the compositions
comprise from less than 10 ppm, preferably, less than 1 ppm, of an
alkali or alkaline earth metal impurity.
[0019] In accordance with the monomer or resin compositions of the
second aspect of the present invention, the
arylcyclobutene-containing monomer or resin contains an addition
polymerizable group, an amine group or two or more aromatic rings
and is chosen from a vinyl phenoxy BCB, vinylnaphthyl BCB, an allyl
phenoxy BCB, an alkynyl phenoxy BCB, a vinyl oligophenoxy BCB, an
allyl oligophenoxy BCB, an aminophenoxy BCB, an amino oligophenoxy
BCB, a novolac phenoxy BCB or an oligophenolic BCB.
[0020] In accordance with the monomer or resin composition of the
second aspect of the present invention, the product preferably
comprises an addition polymerizable group containing
arylcyclobutene monomer having two vinyl groups, wherein Ar is any
of the following formulae (1) to (9), below, and, wherein in the
formulae (1) to (9), below, R=H, CH.sub.3, CH.sub.3CH.sub.2--,
--C(CH.sub.3).sub.2--, --C(CH.sub.3)(CH.sub.2CH.sub.3)--,
--C(Ph.sub.2))--, SO.sub.2 or Ph-, wherein Ph is phenyl:
##STR00005##
[0021] In accordance with the monomer or resin composition of the
second aspect of the present invention, the product preferably
comprises an arylcyclobutene containing oligoaromatic phenol resin
having multiple arylcyclobutene groups of any of the following
formulae (11), below:
##STR00006##
wherein, Z=--CH.sub.2--, --CH.sub.2--CH.sub.2--,
--CH.sub.2--Ar--CH.sub.2--, a C.sub.3 to C.sub.4 alkylene or an
ether, n is an integer from 0 to 8, preferably 0 to 4, and each of
R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7,
R.sub.8, R.sub.9, R.sub.10, and R.sub.11, is independently H,
deuterium, methyl or ethyl, preferably, H.
[0022] In accordance with the monomer or resin compositions of the
second aspect of the present invention, the monomer or resin
compositions comprise the arylcyclobutene-containing addition
polymerizable monomer or the arylcyclobutene-containing aromatic
maleimide monomer and, further, comprise an aromatic addition
polymerizable monomer, such as styrene.
[0023] Unless otherwise indicated, conditions of temperature and
pressure are ambient or room temperature (RT) and standard
pressure. All ranges recited are inclusive and combinable.
[0024] Unless otherwise indicated, any term containing parentheses
refers, alternatively, to the whole term as if no parentheses were
present and the term without them, and combinations of each
alternative. Thus, the term "(meth)acrylate" refers to an acrylate,
a methacrylate, or mixtures thereof.
[0025] As used herein, all amounts are percent by weight and all
ratios are molar ratios, unless otherwise noted.
[0026] All numerical ranges are inclusive of the endpoints and
combinable in any order, except where it is clear that such
numerical ranges are constrained to add up to 100%.
[0027] As used herein, the articles "a", "an" and "the" refer to
the singular and the plural. As used herein, the term "alkyl"
includes linear, branched and cyclic alkyl. Likewise, "alkenyl"
refers to linear, branched and cyclic alkenyl. "Aryl" refers to
aromatic carbocycles and aromatic heterocycles.
[0028] As used herein, the term "aliphatic" refers to an open-chain
carbon-containing moiety, such as alkyl, alkenyl and alkynyl
moieties, which may be linear or branched. Also as used herein, the
term "alicyclic" refers to a cyclic aliphatic moiety, such as
cycloalkyl and cycloalkenyl. Such alicyclic moieties are
non-aromatic, but may include one or more carbon-carbon double
bonds. "Halide" refers to fluoro, chloro, bromo, and iodo. The term
"(meth)acrylate" refers to both methacrylate and acrylate, and
likewise the term (meth)acrylamide refers to both methacrylamide
and acrylamide.
[0029] Unless the context clearly indicates otherwise, by
"substituted" alkyl, alkenyl, or alkynyl is meant that one or more
hydrogens on the alkyl, alkenyl, or alkynyl is replaced with one or
more substituents chosen from halide, hydroxy, C.sub.1-10 alkoxy,
amino, mono- or di-C.sub.1-10 hydrocarbyl substituted amino,
C.sub.5-20 aryl, and substituted C.sub.5-20 aryl.
[0030] Unless the context clearly indicates otherwise, by
"substituted" aryl is meant that one or more hydrogens on the aryl
is replaced by one or more substituents chosen from halide,
hydroxy, C.sub.1-10 alkyl, C.sub.2-10 alkenyl, C.sub.2-10 alkynyl,
C.sub.1-10 alkoxy, amino, mono- or di-C.sub.1-10 hydrocarbyl
substituted amino, C.sub.5-20 aryl, and substituted C.sub.5-20
aryl. "Alkyl" refers to an alkane radical, and includes alkane
diradicals (alkylene) and higher-radicals. Likewise, the terms
"alkenyl", "alkynyl" and "aryl" refer to the corresponding mono-,
di- or higher-radicals of an alkene, alkyne and arene,
respectively.
[0031] As used herein, the term "addition polymerizable group"
means any unsaturation functional group that polymerizes via
addition polymerization, including vinyl, vinylidene or allyl
groups and any such group having any alkyl, alkoxy, S, N, P, O or
Si heteroatom containing hydrocarbon substituent or component, or
any siloxy, cyano, aryl, alkylaryl, S, N, P, O or Si heteroatom
containing aryl group, carbonyl, carboxyl(ate), aldehyde, diketo,
hydroxyl, amine, imine, azo, phosphorus or sulfur containing group
as a substituent or component.
[0032] As used herein, the term "curing" is meant any process, such
as addition crosslinking or condensation, that increases the
molecular weight of a polymer material or composition through the
use of the methods making or using the compositions in accordance
with the present invention. "Curable" refers to any polymer
material capable of being cured under certain conditions.
[0033] As used herein, the term "ASTM" refers to publications of
ASTM International, West Conshohocken, Pa.
[0034] As used herein, the term "DSC" or "Differential Scanning
calorimetry" refers to a method of measuring polymer cure profiles
or exotherms using a Q2000.TM. DSC instrument (TA Instruments, New
Castle, Del.). DSC was carried out using a sample of isolated
uncured polymer (<5 mg) placed in a sealed Tzero.TM. Aluminum
hermetic sample pan (TA instruments). The sample pan was then put
in the DSC cell along with a control pan and the DSC was then
heated from RT to 300.degree. C. at a rate of 10.degree. C. per
minute.
[0035] As used herein, the term "formula weight" refers to the
molecular weight of a representative formula depicting a given
material.
[0036] As used herein, the term "hetero" or "heteroatom" when used
referring to an organic group means an O, P, N, S or Si atom.
[0037] As used herein, the term "NMR" refers to nuclear magnetic
resonance as determined by dissolving from 5 to 100 mg of sample
material in 0.7 ml deuterated chloroform (ACROS Organics, part of
Thermo Fisher Scientific, Pittsburgh, Pa.), then a spectrum was
obtained on a 600 MHz instrument (Bruker BioSpin Corporation,
Billerica, Mass.) or a 500 MHz instrument (Varian, Inc, Palo Alto,
Calif.).
[0038] As used herein, the term "oligomer" refers to relatively low
molecular weight materials such as dimers, trimers, tetramers,
pentamers, hexamers, and the like that are capable of further
curing or polymerization. As used herein, an "oligoaromatic phenol
compound" or "oligoaromatic phenol resin" includes a phenol and one
or more additional aromatic rings and may have up to 30, or,
preferably, up to 10 aromatic or phenyl groups, and may be an
oligophenol, such as a phenol novolac or resole.
[0039] As used herein, the term "organic alkali" means a basic
reaction medium in a polar solvent including alkyl alkali, such as
an alkali alkoxide. An "organic alkali" preferably does not include
added water but may include up to 5,000 ppm of water formed by
hydrolysis or moisture in acidic or amine containing materials.
[0040] As used herein, the term "solids" refers to any materials
that remain a reaction product of the present invention; thus,
solids include monomers and non-volatile additives that do not
volatilize upon any of B-staging, polymerization and cure. Solids
exclude water, ammonia and volatile solvents.
[0041] As used herein, the term "substantially free" of a given
material means that a composition contains 1,000 ppm or less, or,
preferably, 500 ppm or less of that material. As used herein, the
term "anhydrous" means substantially free of water. As used herein,
unless otherwise indicated, the term "weight average molecular
weight" or "Mw" means that value determined by gel permeation
chromatography (GPC) of a polymer solution in tetrahydrofuran (THF)
at room temperature using a Waters Alliance High Pressure Liquid
Chromatogram (HPLC) (Waters, Milford, Mass.) equipped with an
isocratic pump, an autosampler (Injection volume (100-150 .mu.l)
and a Series of 4 Shodex.TM. (8 mm.times.30 cm) columns, each
filled with a polystyrene divinyl benzene (PS/DVB) gel against a
standard calibrated from polystyrene as standards. As used herein,
"number average molecular weight" or "Mn" is measured in the same
way as weight average molecular weight and represents the median
molecular size in a given polymer composition. As used herein, the
term "PDI" refers to the ratio of Mw/Mn.
[0042] As used herein, the term "wt. %" stands for weight
percent.
[0043] As used throughout this specification, the following
abbreviations shall have the following meanings, unless the context
clearly indicates otherwise: .degree. C.=degree Celsius;
min.=minutes; hr.=hours; g=gram; L=liter; .mu.m=micron=micrometer;
nm=nanometer; mm=millimeter; ml=milliliter; MPa=megapascal;
Mw=weight average molecular weight; Mn=number average molecular
weight; AMU=atomic mass unit and ppm is part per million. Unless
otherwise noted, "wt. %" refers to percent by weight, based on the
total weight of a referenced composition.
[0044] In accordance with the present invention,
arylcyclobutene-containing monomers or resins, such as vinyl
phenoxy BCB, allyl phenoxy BCB, amino(oligo)phenol BCB, or
oligoaromatic phenol BCB monomers or resins are synthesized in two
steps from an arylcyclobutene-containing hydrocarbon. The resulting
BCB monomer has ideal curing kinetics for applications benefiting
from addition-ring opening orthogonal curing mechanisms, as
determined by differential scanning calorimetry (DSC). Further, the
monomers can be thermally copolymerized with styrene and other
addition polymerizable monomers via thermal free radical
polymerization at temperatures that allow for subsequent ring
opening cure. Still further, the monomers made by the methods of
the present invention are air and benchtop stable solids at room
temperature. The resulting copolymers also show thermal stability
where other phenoxy resins, such as resorcinol phenoxy BCB have
been shown to decompose.
[0045] In accordance with the methods of the present invention,
deprotection of an organic alkali cleavable protecting group, such
as an alkanoyl group, from an addition polymerizable monomer or
resin, amine group containing monomer or resin or oligoaromatic
compound resin in organic alkali can be followed by reaction with
an alpha-halide (a-halide) or strong acid conjugate leaving group
containing arylcyclobutene compound as a reducing agent. The
deprotection or deacylation reaction is followed by nucleophilic
substitution in the same kettle, vessel or pot. In reacting via
nucleophilic substitution, the contents of the pot are heated to a
temperature of up to 80.degree. C. If the temperature is too high,
the materials might autopolymerize or ring open. However, despite
the relatively mild temperature of reaction, the monomer yields of
methods have heterofore not been attained.
[0046] In accordance with the methods of deprotecting or
deacylating an oligoaromatic phenol compound containing a phenolic
hydroxyl of the present invention, the organic alkali cleavable
protecting group is not a phenolic group. Accordingly, the
oligoaromatic phenol compound containing a phenolic hydroxyl that
results from the deprotecting or deacylating includes one or more
phenolic hydroxyl in addition to the hydroxyl group formed by the
deprotecting or deacylating.
[0047] Preferably, to prevent formation of aldehydes in the product
monomer or resin of the present invention, each of the deprotecting
and the reacting via nucleophilic substitution is carried out in
anhydrous polar media.
[0048] In accordance with the present invention, the methods are
suitable for making addition polymerizable monomer materials, such
as addition polymerizable arylcyclobutene-containing monomers
having one or more aryloxy, such as phenoxy, aminophenol, amino
oligophenol or oligophenolic groups. The methods in accordance with
the present invention are also useful in making arylcyclobutene
compounds containing aromatic amine functional groups or
oligoaromatic phenol resins. Preferably, the methods of making
monomer or resin materials in accordance with the present invention
provide addition polymerizable arylcyclobutene compound having one
or more aryloxy, such as phenoxy, oligophenolic groups.
[0049] In addition, the methods in accordance with the present
invention can provide amine containing arylcyclobutene-containing
monomers having one or more aryloxy, such as phenoxy, or
oligophenolic groups; and the methods in accordance with the
present invention can provide novolac or phenolic resin containing
arylcyclobutene compounds.
[0050] The methods comprise reacting an alpha-halide (a-halide) or
strong acid conjugate arylcyclobutene-containing compound, such as
a 1-bromobenzocyclobutene (a Br BCB), with a phenol or an
oligophenol containing an amine functional group, an addition
polymerizable group, such as vinyl phenol, or an oligophenol
containing compound, such as a phenolic resin. The phenol or
oligophenol is itself formed by deprotecting an addition
polymerizable aromatic monomer, aromatic amine containing monomer
or oligaromatic compound containing an organic alkali cleavable
protecting group, such as acetoxystyrene or acetoxyaniline.
[0051] Preferably, the monomer composition of the present invention
may comprise a monomer B having the Structure B, below:
##STR00007##
wherein K is a divalent group chosen from a divalent aryloxy group
having from 1 to 10, or, preferably, from 1 to 6 aryl or phenol
rings, or, preferably, from 1 to 6 aryl or phenol rings, or an
oligophenolic group having from 1 to 10, r, preferably, from 1 to 6
phenol units;
[0052] M is a divalent aromatic group chosen from a C.sub.1 to
C.sub.6 alkyl substituted or unsubstituted aromatic radical group,
or a C.sub.1 to C.sub.6 alkyl substituted or unsubstituted divalent
heteroaromatic radical group;
[0053] L.sub.1 is a covalent bond; and,
[0054] R.sub.1 through R.sub.6 are each independently selected from
a monovalent group chosen from hydrogen, deuterium, halide,
hydroxyl, a C.sub.1 to C.sub.6 alkyl group, a C.sub.1 to C.sub.6
alkoxy group, a C.sub.1 to C.sub.6 alkyl substituted hydrocarbon
group, a heteroatom containing hydrocarbon group, a C.sub.1 to
C.sub.6 alkyl substituted heterohydrocarbon group, a cyano group,
or an hydroxyl group, or preferably, each of R.sub.1, R.sub.2 and
R.sub.3 is a hydrogen, or, more preferably, each of R.sub.1 through
R.sub.6 is a hydrogen.
[0055] Preferably, the methods of the present invention provide a
monomer composition, such as one comprising vinyl phenoxy BCB in
which the polymerizable group is connected the four membered BCB
ring, as shown in formula I, below. The monomer is
7-((4-vinylbenzyl)oxy)bicyclo[4.2.0]octa-1(6),2,4-triene. The
present invention also enables the provision of a copolymer, such
as a styrene-co-vinyl phenoxy BCB.
##STR00008##
[0056] In accordance with the monomer compositions of the present
invention, addition polymerizable monomer mixtures of one or more
addition polymerizable arylcyclobutene-containing monomers A having
one or more aryloxy, or oligophenolic group, one or more aromatic
addition polymerizable second monomers, and, if desired, one or
more other addition polymerizable monomers chosen from an addition
polymerizable nitrogen heterocycle containing third monomer, an
addition polymerizable fourth monomer, or, preferably, both of the
one or more third monomers and the one or more fourth monomers.
[0057] The monomer compositions are suitable for forming polymers
by addition polymerization, such as at temperatures of from ambient
temperature to 140.degree. C. The resulting polymers find use in
making, for example, thin films, coatings or bulk dielectric
materials, which can be dried or soft baked at from 60 to
140.degree. C., followed by ring opening cure at from 140 to
220.degree. C.
EXAMPLES
[0058] The present invention will now be described in detail in the
following, non-limiting Examples:
[0059] Unless otherwise stated all temperatures are room
temperature (21-23.degree. C.) and all pressures are atmospheric
pressure (-760 mm Hg or 101 kPa).
[0060] Notwithstanding other raw materials disclosed below, the
following raw materials were used in the Examples:
[0061] BCB: benzocyclobutene;
[0062] DMF: dimethylformamide;
[0063] THF: tetrahydrofuran; and,
[0064] V601: A diazo radical initiator, dimethyl
2,2'-azobis(2-methylpropionate (CAS No 2589-57-3, Wako Chemical,
Japan).
Comparative Example 1: Preparation of Vinyl Phenyl
Benzocyclobutene
[0065] In the following example, as shown by the equation, below a
Grignard reagent undergoes a catalyst mediated coupling to a
palladium intermediate to form vinylphenyl BCB in a poor yield.
##STR00009##
[0066] Magnesium turnings (210 mg), sodium hydride (29 mg, 60% oil
dispersion) and a magnetic stir bar were added to a 100 ml rbf,
capped with a rubber septum and placed under vacuum and allowed to
stir for 4 hours. A solution of BrBCB (750 mg) in THF (20 ml) was
added via syringe slowly. The solution turned bright yellow and was
placed under a nitrogen atmosphere. The solution was left to stir
for 30 minutes then added via syringe to a 100 ml rbf containing a
stir bar, bromostyrene (1 g), Pd PEPPSI-iPr
(1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene)(3-chloropyridyl)pallad-
ium(II) dichloride, CAS no: 905459-27-0) catalyst (190 mg, 5 mol %)
and THF (15 ml) under nitrogen and capped with a rubber septum. The
mixture turned black after about 30 minutes and was left to stir at
room temperature for 12 h. The mixture was added to a separatory
funnel containing water (100 ml), and extracted with ethyl acetate
(3.times.100 ml). The combined organics were dried with brine (100
ml) and sodium sulfate, filtered and concentrated in vacuo. The
residue was recrystallized in methanol to give the desired product
as a colorless solid (203 mg, 18% yield). 1H NMR (500 MHz,
Chloroform-d) .sigma. 7.49 (d, J=8.1 Hz, 2H), 7.44-7.26 (m, 6H),
6.84 (dd, J=17.7, 10.8 Hz, 1H), 5.86 (d, J=17.7 Hz, 1H), 5.35 (d,
J=10.8 Hz, 1H), 4.86-4.75 (m, 1H), 3.85 (dd, J=13.9, 5.7 Hz, 1H),
3.22 (dd, J=13.9, 2.7 Hz, 1H). A DSC of the resulting monomer
showed an exotherm (cure) peak max of 165.degree. C. at a scan rate
of 10.degree. C./min.
[0067] The yield in the above reaction was very low. Further, no
ether linkage resulted from the reaction. However, the cure
temperature of the monomer was acceptable.
Example 2: Preparation of Vinyl Phenoxy Benzocyclobutene
[0068] In a 250 ml three necked round bottom flask equipped with a
polytetraflouroethylene (Teflon.TM. polymer, Dupont, Wilmington,
Del.) coated magnetic stir bar, potassium hydroxide (1.38 g, 1 eq)
was dissolved in water (6.83 g). Then, 4-acetoxy styrene (4 g, 1
eq) was added dropwise at room temperature, and the solution turned
from colorless to pale orange. Potassium carbonate (6.82 g, 2 eq)
was added portionwise, and the solution was stirred for one hour.
The flask was equipped with a reflux condenser, then
1-bromobenzocyclobutene (4.06 g, 1 eq) was added dropwise in DMF
(41 ml). The solution was then heated to 70.degree. C. and allowed
to reflux overnight. To the reaction was added water (50 ml) and
ethyl acetate (50 ml). The aqueous residue was extracted four times
with ethyl acetate (100 ml). The combined organics were extracted
with sodium bicarbonate solution (1.times.100 ml), lithium chloride
aqueous solution (1.times.100 ml) and brine (2.times.100 ml). The
organics were dried over sodium sulfate, filtered and concentrated
in vacuo to give the product as a of white solid (3.36 g, 68%
yield). Melting point 54-60.degree. C. 1H NMR (600 MHz,
Chloroform-d) .sigma. 7.39 (d, J=8.6 Hz, 2H), 7.34 (td, J=7.3, 1.5
Hiz, 1H), 7.31-7.24 (m, 2H), 7.21-7.18 (m, 1H), 6.98 (d, J=8.6 Hz,
2H), 6.69 (dd, J=17.6, 10.9 Hz, 1H), 5.70 (dd, J=4.3, 1.9 Hz, 1H),
5.64 (dd, J=17.6, 0.9 Hz, 1H), 5.15 (dd, J=10.9, 0.9 Hz, 1H), 3.73
(dd, J=14.2, 4.3 Hz, 1H), 3.31 (d, J=14.2 Hz, 1H). 13C NMR (151
MHz, Chloroform-d) .sigma. 157.79, 144.62, 142.57, 136.20, 130.87,
129.93, 127.50, 127.43, 123.48, 123.04, 115.06, 111.80, 74.28,
39.45. Yield from the above example was good and the resulting
monomer was a stable solid which has a desirable ring opening cure
temperature of 184.degree. C.
Example 3: Preparation of Vinyl Phenoxy Benzocyclobutene
[0069] To a 3 L three neck reaction flask fitted with mechanical
stirring (300 rpm), a glass addition funnel and a thermocouple was
added acetoxystyrene and DMF. The acetoxystyrene was sparged with
nitrogen for 15 minutes, then the reactor was submerged in an ice
bath to which the thermocouple read 15.degree. C. A solution of
sodium methoxide in methanol (NaOMe/MeOH) was fed into the glass
addition funnel, and the solution was added portion-wise over 60
minutes, monitoring the exotherm (highest T was 21.degree. C.).
When addition was complete, a wine red solution was observed.
1-BrBCB, DMF and a nitroxide containing radical polymerization
inhibitor (TEMPO, 2,2,6,6-Tetramethylpiperidine 1-oxyl, CAS
2564-83-2, 25 mg) were fed into the reactor and stirred for 30
minutes. The ice bath was removed and a heating mantle was applied.
The mixture was heated to 70.degree. C. (setpoint, never exceeded
70.degree. C.). The mixture was stirred and tracked by NMR (d6 DMSO
or d6 acetone) and was complete after 18 h. The solution darkened
and a few particulates were observed. The reactor was allowed to
cool to 35.degree. C., then 450 ml water was added and stirred for
10 minutes.
[0070] The mixture was transferred to a large separation funnel,
and organics were dissolved after 6000 ml of a mixture of heptanes
had been added with some agitation. The bottom aqueous layer was
drained and an NMR was taken to look for remaining organic
material, which was not observed.
[0071] The organic layer was drained and stripped in vacuo wherein
product was placed in 4 glass jars and cycled in vacuum 10 times
over 3 days at RT to dry.
[0072] The dry product was a tan solid 586.02 g, an excellent 96%
yield, 99% purity by UPLC. The melting point and NMR spectra of the
resulting monomer, 4-vinylphenoxy BCB, matched the product isolated
in Example 2, above.
Comparative Example 4: Preparation of 4-amino phenoxy BCB
[0073] In a 250 ml rbf with magnetic stir bar was added aminophenol
(1 g, 1 eq), THF (15 ml) and KOtBu (1.23 g, 1.2 eq). The mixture
was allowed to stir for 1 hour at room temperature. Bromo BCB (1.68
g, 1 eq) was added in THF (15 ml). The reaction was capped and
allowed to stir for 12 h at room temperature. Water (100 ml) was
then added. Ethyl acetate (3.times.100 ml) was used to extract the
product from the aqueous phase. The combined organics were dried
over sodium sulfate, filtered and concentrated in vacuo. The crude
residue was subjected to a column of silica gel using heptanes and
ethyl acetate (9:1) as eluent to give product (892 mg, 46%) as a
dark oil.
[0074] 1H NMR (500 MHz, Chloroform-d) .sigma. 7.32 (dt, J=6.6, 4.3
Hz, 1H), 7.28-7.23 (m, 2H), 7.18 (d, J=7.4 Hz, 1H), 6.86 (d, J=9.0
Hz, 2H), 6.69 (d, J=9.0 Hz, 2H), 5.59 (dd, J=4.3, 2.1 Hz, 1H), 3.66
(dd, J=14.1, 4.3 Hz, 1H), 3.46 (br s, 2H), 3.28 (d, J=14.1 Hz, 1H).
13C NMR (126 MHz, Chloroform-d) .sigma. 151.04, 145.18, 142.64,
140.49, 129.73, 127.29, 123.47, 123.00, 116.48, 116.36, 74.89,
39.47. DSC Showed an exotherm peak temperature at 179.degree. C. at
a scan rate of 10.degree. C./min.
[0075] The procedure in Example 2 can be followed to produce the
following products from the corresponding unsaturated starting
materials shown in the table, below:
TABLE-US-00001 Organic Alkali Cleavable protecting Group Containing
Example Monomer Product 5 ##STR00010## ##STR00011## 6 ##STR00012##
##STR00013## 7 ##STR00014## ##STR00015## 1.
Propane-2,2-diylbis(2-allyl)-4,1-phenylene) diacetate; 2.
7,7'-((propane-2,2-diylbis(2-allyl)-4,1-phenylene))bis(oxy))bis(bicyclo-
[4.2.0]octa-1,3,5-triene); 3. 3,5-diethynylphenyl acetate; 4.
7-(3,5-diethynylphenoxy)bicyclo[4.2.0]octa-1(6),2,4-triene; 5.
3,3'-diallyl-[1,1-biphenyl]-4,4'-diyl diacetate; 6.
7,7'-((3,3'-diallyl-[1,1'-biphenyl]-4,4'-diyl)bis(oxy))bis(bicyclo[4.2.-
0]octa-1(6),24-trien).
Example 8: Preparation of a Copolymer of Vinyl Phenoxy
Benzocyclobutene Co Styrene
[0076] Styrene (4.77 g) and vinyl phenoxy benzocyclobutene (1.13 g)
were dissolved in THF (3.98 g) along with V601.TM. initiator (70
mg) in an EZ Max.TM. 100 ml jacketed reactor (Mettler Toledo,
Columbia, Md.) equipped with overhead stirring and nitrogen
atmosphere. The solution was purged with nitrogen gas for 30
minutes, then heated to an internal temperature of 60.degree. C.
overnight. The resulting viscous solution was diluted with THF (20
ml) then precipitated into methanol (250 ml), filtered and dried
overnight in vacuo to give the copolymer (4.23 g, 72% yield). Mn
36.6k, Mw 79.1k. The polymer curing kinetics were evaluated via
differential scanning calorimetry (DSC, TA Instruments Q2000, TA
instruments, New Castle, Del.) at a ramp rate of 2, 5, 10 and
20.degree. C./min. The Kissinger method was used to determine a
ring opening activation barrier of 24.2 kcal/mol. Thermal stability
was evaluated using thermogravimetric analysis (TA Instruments
Q5000) under a nitrogen atmosphere, wherein a solid polymer sample
was placed in a TGA pan and run out to 400.degree. C. at a rate of
10.degree. C./min.
[0077] The TGA of the resulting copolymer exhibited a five percent
weight loss value at 300.degree. C.
* * * * *