U.S. patent number RE40,508 [Application Number 10/641,029] was granted by the patent office on 2008-09-16 for thermally stable polymers, method of preparation, and articles made therefrom.
This patent grant is currently assigned to SABIC Innovative Plastics IP B.V.. Invention is credited to Daniel Joseph Brunelle, Taeseok Jang, Gregory Allen O'Neil, Edward Pickett, Tiberiu Mircea Sielovan, Joseph Anthony Suriano.
United States Patent |
RE40,508 |
Brunelle , et al. |
September 16, 2008 |
Thermally stable polymers, method of preparation, and articles made
therefrom
Abstract
Thermally stable polymers comprising resorcinol arylate chain
members are prepared using an interfacial method comprising the
steps of: (a) combining at least one resorcinol moiety and at least
one catalyst in a mixture of water and at least one organic solvent
substantially immiscible with water; and (b) adding to the mixture
from (a) at least one dicarboxylic acid dichloride while
maintaining the pH between 3 and 8.5 through the presence of an
acid acceptor, wherein the total molar amount of acid chloride
groups is stoichiometrically deficient relative to the total molar
amount of phenolic groups.
Inventors: |
Brunelle; Daniel Joseph (Burnt
Hills, NY), Suriano; Joseph Anthony (Clifton Park, NY),
Jang; Taeseok (Troy, NY), Sielovan; Tiberiu Mircea
(Schenectady, NY), Pickett; Edward (Schenectady, NY),
O'Neil; Gregory Allen (Schenectady, NY) |
Assignee: |
SABIC Innovative Plastics IP
B.V. (Bergen op Zoom, NL)
|
Family
ID: |
26832584 |
Appl.
No.: |
10/641,029 |
Filed: |
August 15, 2003 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
09368706 |
Aug 5, 1999 |
6306507 |
|
|
|
60134692 |
May 18, 1999 |
|
|
|
Reissue of: |
09656208 |
Sep 6, 2000 |
06291589 |
Sep 18, 2001 |
|
|
Current U.S.
Class: |
525/165; 528/176;
525/88; 528/274; 528/64; 528/198; 528/196; 525/133 |
Current CPC
Class: |
B32B
27/36 (20130101); C08G 63/79 (20130101); C08G
63/6956 (20130101); B32B 27/08 (20130101); C09D
167/03 (20130101); B32B 27/18 (20130101); C08G
63/85 (20130101); C08G 63/676 (20130101); B32B
27/20 (20130101); C08G 63/19 (20130101); C08J
7/046 (20200101); C08G 63/64 (20130101); B32B
27/365 (20130101); C08J 7/0427 (20200101); B32B
27/06 (20130101); C08J 7/043 (20200101); Y10T
428/31565 (20150401); Y10T 428/31507 (20150401); Y10T
428/2942 (20150115); Y10T 428/31786 (20150401); B32B
2605/00 (20130101); C08J 2467/00 (20130101); B32B
2369/00 (20130101); Y10T 428/254 (20150115); Y10T
428/1355 (20150115); B32B 2367/00 (20130101); F02B
61/045 (20130101); B32B 2307/4026 (20130101); Y10T
428/25 (20150115); Y10T 428/1359 (20150115) |
Current International
Class: |
C08L
67/02 (20060101) |
Field of
Search: |
;525/165,88,133
;528/104,176,196,198,274 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Other References
DE Pub. No. 1927938; Publication Date: Dec. 3, 1970; Abstract Only;
1 page. cited by other .
JP Patent No. 58035615; Publication Date: Mar. 2, 1983; Abstract
Only; 1 page. cited by other .
JP Patent No. 3065177; Publication Date: Mar. 20, 1991; Abstract
Only; 1 page. cited by other .
JP Patent No. 3067449; Publication Date: Mar. 22, 1991; Abstract
Only; 2 pages. cited by other .
JP Patent No. 06122756; Publication Date: May 6, 1994; Abstract
Only; 1 page. cited by other.
|
Primary Examiner: Truong; Duc
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
.Iadd.This application is a REI of Ser. No. 09/656,208 filed Sep.
6, 2000 now U.S. Pat. No. 6,291,589, which is a DIV of Ser. No.
09/368,706 filed Aug. 5, 1999 now U.S. Pat. No. 6,306,507, which
claims benefit of 60/134,692 filed May 18, 1999..Iaddend.
This application is a division of application Ser. No. 09,368,706,
filed Aug. 5, 1999, which is hereby incorporated by reference in
its entirety.
This application claims the benefit of U.S. Provisional Application
No. 60/134,692, filed May 18, 1999.
Claims
What is claimed is:
1. A block copolymer consisting essentially of resorcinol arylate
polyester segments in combination with organic carbonate segments,
substantially free of anhydride linkages linking at least two mers
of the polymer chain, prepared by an interfacial method, comprising
the steps of: (a) combining at least one resorcinol moiety and at
least one catalyst in a mixture of water and at least one organic
solvent substantially immiscible with water; and (b) adding to the
mixture from (a) at least one dicarboxylic acid dichloride while
maintaining the pH between 3 and 8.5 through the presence of an
acid acceptor, wherein the total molar amount of acid chloride
groups is stoichiometrically deficient relative to the total molar
amount of phenolic groups.
2. The copolymer of claim 1, prepared by an interfacial method
further comprising the step of: adjusting the pH of the reaction
mixture to between 7 and 12 following addition of the at least one
dicarboxylic acid dichloride.
3. The copolymer of claim 2, prepared by an interfacial method
further comprising the step of: stirring the reaction mixture for
at least 3 minutes at pH between 7 and 12.
4. The copolymer of claim 1 wherein the at least one resorcinol
moiety is selected from the group consisting of unsubstituted
resorcinol, 2-methyl resorcinol, and mixtures thereof.
5. The copolymer of claim 4 wherein the at least one resorcinol
moiety is unsubstituted resorcinol.
6. The copolymer of claim 1 wherein the at least one dicarboxylic
acid dichloride is at least one member selected from the group
consisting of isophthaloyl dichloride, terephthaloyl dichloride,
naphthalene-2,6-dicarboxylic acid dichloride, sebacoyl chloride,
cyclohexane-1,4-dicarboxylic acid dichloride and mixtures
thereof.
7. The copolymer of claim 6 wherein the at least one dicarboxylic
acid dichloride is a mixture of isophthaloyl dichloride and
terephthaloyl dichloride.
8. The copolymer of claim 7 wherein the ratio of isophthaloyl
dichloride to terephthaloyl dichloride is about 0.2-5:1.
9. The copolymer of claim 8 wherein the ratio of isophthaloyl
dichloride to terephthaloyl dichloride is about 0.8-2.5:1.
10. The copolymer of claim 8 wherein the stoichiometric ratio of
total phenolic groups to total acid chloride groups is about
1.5-1.01:1.
11. The copolymer of claim 10 wherein the stoichiometric ratio of
total phenolic groups to total acid chloride groups is about
1.2-1.02:1.
12. The copolymer of claim 1 prepared by an interfacial method
wherein the pH is maintained using an alkali metal hydroxide, an
alkaline earth hydroxide, or an alkaline earth oxide.
13. The copolymer of claim 12 prepared by an interfacial method
wherein the pH is maintained using aqueous sodium hydroxide.
14. The copolymer of claim 1 wherein the organic carbonate segments
comprise at least one dihydroxy-substituted aromatic
hydrocarbon.
15. The copolymer of claim 14 wherein the dihydroxy-substituted
aromatic hydrocarbon is bisphenol A.
16. The copolymer of claim 14 further comprising at least one
chain-stopper selected from the group consisting of mono-phenolic
compounds, mono-carboxylic acid chlorides, mono-chloroformates, and
mixtures thereof.
17. The copolymer of claim 1 wherein the molecular weight of said
copolymer decreases by less than 12% upon heating said polymer at a
temperature of about 280-290.degree. C. for five minutes.
18. The copolymer of claim 17 wherein the molecular weight of said
copolymer decreases by less than 5% upon heating at a temperature
of about 280-290.degree. C. for five minutes.
19. A block copolymer consisting essentially of resorcinol arylate
polyester segments in combination with organic carbonate segments,
substantially free of anhydride linkages linking at least two mers
of the polymer chain, prepared by an interfacial method, comprising
the steps of: (a) combining at least one of unsubstituted
resorcinol and 2-methylresorcinol; and at least one catalyst
selected from the group consisting of quaternary ammonium salts and
tertiary amines, in a mixture of water and dichloromethane; (b)
adding to the mixture from (a) a mixture of isophthaloyl dichloride
and terephthaloyl dichloride in a molar ratio of isophthalate to
terephthalate of 0.4-2.5-1, while maintaining the pH between 3 and
8.5 through addition of aqueous sodium hydroxide, wherein the ratio
of moles total .[.acid chloride groups to moles total phenolic.].
.Iadd.phenolic groups to moles total acid chloride .Iaddend.groups
is 1.5-1.01:1; (c) adjusting the pH of the reaction mixture to
between 8.5 and 12 following addition of the dicarboxylic acid
dichloride mixture, and stirring the reaction mixture for at least
3 minutes at said pH; (d) combining the product from (c) with at
least one diphenol, at least one mono-phenolic chain-stopper, and
phosgene under basic conditions; and (.[.d.]. .Iadd.e.Iaddend.)
isolating the copolymer, said copolymer decreasing in molecular
weight by less than 12% upon heating at a temperature of about
280-290.degree. C. for five minutes.
.Iadd.20. A block copolymer consisting essentially of resorcinol
arylate polyester segments in combination with organic carbonate
segments, substantially free of anhydride linkages linking at least
two mers of the polymer chain, prepared by an interfacial method,
comprising the steps of: (a) combining at least one of
unsubstituted resorcinol and 2-methylresorcinol; and at least one
catalyst selected from the group consisting of quaternary ammonium
salts and tertiary amines, in a mixture of water and
dichloromethane; (b) adding to the mixture from (a) a mixture of
isophthaloyl dichloride and terephthaloyl dichloride in a molar
ratio of isophthalate to terephthalate of 0.4-2.5-1, while
maintaining the pH between 3 and 8.5 through addition of aqueous
sodium hydroxide, wherein the ratio of moles total phenolic groups
to moles total acid chloride groups is 1.5-1.01:1; (c) adjusting
the pH of the reaction mixture to between 8.5 and 12 following
addition of the dicarboxylic acid dichloride mixture, and stirring
the reaction mixture for at least 3 minutes at said pH; (d)
combining the product from (c) with at least one
dihydroxy-substituted aromatic hydrocarbon, at least one
mono-phenolic chain-stopper, and phosgene under basic conditions;
and (e) isolating the copolymer, said copolymer decreasing in
molecular weight by less than 12% upon heating at a temperature of
about 280-290.degree. C. for five minutes..Iaddend.
Description
BACKGROUND OF THE INVENTION
This invention relates to thermally stable polymers comprising
resorcinol arylate polyester chain members, a method for their
preparation, and multilayer articles made therefrom.
Various polymeric articles have a problem of long term color
instability. In many cases this instability is seen as yellowing of
the polymer, detracting from its attractiveness and also
transparency when the polymer was initially transparent. Loss of
gloss can also be an undesirable long term phenomenon.
Yellowing of polymers is often caused by the action of ultraviolet
radiation, and such yellowing is frequently designated
"photoyellowing". Numerous means for suppressing photoyellowing
have been employed and proposed. Many of these involve
incorporation in the polymer of ultraviolet absorbing compounds
(UVA's). For the most part, UVA's are low molecular weight
compounds, which must be employed at relatively low levels,
typically up to 1% by weight, to avoid degradation of the physical
properties of the polymer such as impact strength and high
temperature properties as reflected in heat distortion temperature.
Another problem of concern with polymers such as aromatic
polycarbonates and addition polymers of alkenylaromatic compounds
such as styrene is susceptibility to attack by organic liquids.
One way of protecting a resinous article against photoyellowing and
loss of gloss is to apply a coating of a weatherable second
polymer, the term "weatherable" as used herein signifying
resistance to such phenomena. Coatings made from polyesters
containing resorcinol arylate units often possess good
weatherability properties. The arylate moieties typically contain
isophthalate, terephthalate, and especially mixtures of iso- and
terephthalate units. Polyesters of resorcinol with mixtures of
isophthalate and terephthalate chain members typically have good
weatherability properties and may provide protection against
photoyellowing when coated over a resinous substrate.
The good weatherability properties of polyesters containing
resorcinol arylate units are believed to arise in large part from
the screening effect said polymers may provide to ultraviolet (UV)
light. On exposure to UV light polymers comprising resorcinol
arylate chain members may undergo photochemical Fries rearrangement
converting at least a portion of the polymer from polyester chain
members to o-hydroxybenzophenone-type chain members. The
o-hydroxybenzophenone-type chain members act to screen further UV
light and protect UV-sensitive components in a resorcinol
arylate-containing composition. The good weatherability properties
of polymers comprising resorcinol arylate chain members make them
especially useful in blends and in multilayer articles in which
said polymers may act as a protecting layer for more sensitive
substrate components.
Copolyesters comprising resorcinol iso- and terephthalate polyester
chain members in combination with diacid or diol alkylene chain
members (so-called "soft-block" chain members) are disclosed in
U.S. Pat. No. 5,916,997. These copolymers have excellent
weatherability and flexibility. Copolyestercarbonates comprising
resorcinol iso- and terephthalate polyester chain members in
combination with carbonate chain members are disclosed in commonly
owned, co-pending application Ser. No. 09/181,902 (now abandoned).
These copolymers have excellent weatherability and are compatible
with polycarbonates in blends.
Polyesters containing resorcinol arylate chain members have been
prepared by melt methods as disclosed in U.S. Pat. No. 4,127,560
and in Japanese Kokai 1/201,326. The methods may provide polyesters
containing isophthalate and terephthalate chain members but do not
allow the incorporation of greater than 30 mole % terephthalate. In
addition, the polyesters obtained have unacceptable color.
Polyesters containing resorcinol arylate chain members have also
been prepared by an interfacial method. The interfacial method
comprises a solvent mixture containing water and at least one
organic solvent substantially immiscible with water. According to
U.S. Pat. No. 3,460,961 and Eareckson, Journal of Polymer Science,
vol. XL, pp. 399-406 (1959), preparation of resorcinol arylate
polyesters with a mixture of iso- and terephthalate chain members
is performed by an interfacial method in water and a
water-immiscible solvent such as chloroform or dichloromethane
using 1:1 stoichiometric ratio of resorcinol to either iso- or
terephthaloyl dichloride or a mixture thereof, in the presence of
aqueous sodium hydroxide. The resorcinol is combined with the
aqueous sodium hydroxide before addition of acid chlorides, and the
reaction is run at pH which is initially high but which decreases
as the reaction proceeds. The molecular weight of the polymers is
not controlled. The method provides polymer with very high weight
average molecular weight (Mw), making the polymer unsuitable for
some applications. Furthermore, the polymer has poor thermal
stability and loses molecular weight upon thermal treatment.
Multilayer articles containing layers made from resorcinol
arylate-containing polyester have been described by Cohen et al.,
Journal of Polymer Science: Part A-1, vol. 9, 3263-3299 (1971) and
in U.S. Pat. No. 3,460,961. The polyester was made either in
solution or by an interfacial process. The solution method requires
the use of a stoichiometric amount of an organic base, such as a
tertiary amine, which must be isolated and recovered for reuse in
any economical, environmentally friendly process. Both methods
produce thermally unstable polyester which can only be applied by
solution coating followed by evaporation of the solvent to make a
multilayer article. This solution coating method has numerous
deficiencies, some of which are mentioned in the Cohen et al. paper
at page 3267: namely, the necessity to use high priced and toxic
solvents, the inherently low concentration of the arylate polymer
in the solvent and the tendency of the solutions to gel.
Accordingly, the described polyesters were considered "unacceptable
coating candidates".
Japanese Kokai 1/199,841 discloses articles having a substrate
layer comprising at least 90 mole percent poly (ethylene
terephthalate) and a gas barrier coating layer which is a polyester
of resorcinol and a minimum of 50 mole % isophthalic acid,
optionally with copolyester units derived from another dicarboxylic
acid such as terephthalic acid, naphthalenedicarboxylic acid or
various other specifically named dicarboxylic acids. The disclosed
articles may be prepared by a series of operations including
co-injection molding. However, the only types of articles disclosed
are bottles, which are produced from a co-injection molded parison
by subsequent blow molding. Larger articles, such as external
automobile body parts, are not disclosed and no method for their
production is suggested, nor are articles in which the substrate
layer is anything other than poly (ethylene terephthalate). In
addition, the resorcinol isophthalate polyesters were prepared
either by melt methods which do not allow the incorporation of
greater than 30 mole % terephthalate and give polyester with
unacceptable color, or by the interfacial method which produces
thermally unstable polyester.
It remains of interest, therefore, to develop a method for
preparing weatherable, solvent resistant multilayer articles which
are capable of use for such varied purposes as body parts for
outdoor vehicles and devices such as automobiles. There is also a
particular need for polymers comprising resorcinol arylate chain
members having controlled molecular weight, high thermal stability,
and low color. There is also a particular need for polymers
comprising resorcinol arylate chain members that can be processed
using typical melt processing techniques.
BRIEF SUMMARY OF THE INVENTION
The present inventors have identified the primary source of poor
thermal stability in polymers comprising resorcinol arylate
polyester chain members prepared by the interfacial method, and
have discovered a method to prepare said polymers in thermally
stable form with controlled molecular weight. The new method also
allows the preparation of virtually colorless polymers comprising
resorcinol arylate polyester chain members.
In one of its aspects the present invention provides an interfacial
method for preparing polymers comprising resorcinol arylate
polyester chain members substantially free of anhydride linkages
linking at least two mers of the polymer chain, comprising the
steps of: (a) combining at least one resorcinol moiety and at least
one catalyst in a mixture of water and at least one organic solvent
substantially immiscible with water; and (b) adding to the mixture
from (a) at least one dicarboxylic acid dichloride while
maintaining the pH between 3 and 8.5 through the presence of an
acid acceptor, wherein the total molar amount of acid chloride
groups is stoichiometrically deficient relative to the total molar
amount of phenolic groups.
In another of its aspects the invention provides a polymer
consisting essentially of resorcinol arylate polyester chain
members substantially free of anhydride linkages linking at least
two mers of the polymer chain, prepared by an interfacial method
comprising the above steps.
In yet another of its aspects the invention provides a copolymer
consisting essentially of resorcinol arylate polyester chain
members in combination with C.sub.3-20 straight chain alkylene,
C.sub.3-10 branched alkylene, or C.sub.4-10 cyclo- or
bicycloalkylene chain members, substantially free of anhydride
linkages linking at least two mers of the polymer chain, prepared
by an interfacial method comprising the above steps.
In still another of its aspects the invention provides a copolymer
consisting essentially of resorcinol arylate polyester chain
members in combination with organic carbonate chain members,
substantially free of anhydride linkages linking at least two mers
of the polymer chain, prepared by an interfacial method, comprising
the above steps.
DETAILED DESCRIPTION OF THE INVENTION
In one embodiment the present invention comprises an interfacial
method for preparing thermally stable polymers comprising
resorcinol arylate polyester chain members which derive their
thermal stability in large part from being substantially free of
anhydride linkages in the polymer chains. In another embodiment the
present invention comprises the thermally stable polymers prepared
by such an interfacial method.
Thermal stability within the context of the present invention
refers to resistance of a polymer to molecular weight degradation
under thermal conditions. Thus, a polymer with poor thermal
stability shows significant molecular weight degradation under
thermal conditions, such as during extrusion, molding,
thermoforming, hot-pressing, and like conditions. Molecular weight
degradation may also be manifest through color formation and/or in
the degradation of other properties such as weatherability, gloss,
mechanical properties, and/or thermal properties. Molecular weight
degradation can also cause significant variation in processing
conditions as the melt viscosity changes.
In one of its aspects the method of the present invention provides
thermally stable polymers comprising arylate polyester chain
members. Said chain members comprise at least one diphenol residue
in combination with at least one aromatic dicarboxylic acid
residue. The preferred diphenol residue, illustrated in Formula I,
is derived from a 1,3-dihydroxybenzene moiety, commonly referred to
throughout this specification as resorcinol or resorcinol moiety.
Resorcinol or resorcinol moiety as used within the context of the
present invention should be understood to include both
unsubstituted 1,3-dihydroxybenzene and substituted,
1,3-dihydroxybenzenes unless explicitly stated otherwise.
##STR00001## In Formula I R is at least one of C.sub.1-12 alkyl or
halogen, and n is 0-3.
Suitable dicarboxylic acid residues include aromatic dicarboxylic
acid residues derived from monocyclic moieties, preferably
isophthalic acid, terephthalic acid, or mixtures of isophthalic and
terephthalic acids, or from polycyclic moieties, including diphenyl
dicarboxylic acid, diphenylether dicarboxylic acid, and
naphthalenedicarboxylic acid, preferably
naphthalene-2,6-dicarboxylic acid.
Preferably, the aromatic dicarboxylic acid residues are derived
from mixtures of isophthalic and/or terephthalic acids as typically
illustrated in Formula II. ##STR00002##
Therefore, in one embodiment the present invention provides
thermally stable polymers comprising resorcinol arylate polyester
chain members as typically illustrated in Formula III wherein R and
n are as previously defined: ##STR00003##
Previous interfacial methods for preparing polyesters comprising
resorcinol arylate chain members typically provide polymers with
poor thermal stability and uncontrolled molecular weight. The
present inventors have discovered that a primary reason for poor
thermal stability is the presence of anhydride linkages in the
backbone of the polyester chain. Typical anhydride linkages are
illustrated in Formula IV. Such anhydride linkages link at least
two mers in a polymer chain and may arise through combination of
two isophthalate or terephthalate moieties or mixtures thereof,
although it is to be understood that anhydride linkages in polymers
comprising resorcinol arylate chain members may arise through
combination of any suitable similar dicarboxylic acid residues or
mixtures of suitable dissimilar dicarboxylic acid residues present
in a reaction mixture. ##STR00004##
Although the invention is not limited by theory, it is believed
that the anhydride linkage represents a weak bond in the polyester
chain, which can break under thermal processing conditions to
produce shorter chains terminated by acid end-groups. These acid
end-groups, in turn, may accelerate the hydrolysis of the arylate
moiety, generating additional carboxyl and hydroxyl end-groups, and
further contributing to the molecular weight degradation, and loss
in other desirable properties. Anhydride linkages may arise through
several mechanisms. In one mechanism a carboxylic acid chloride may
be hydrolyzed to carboxylic acid when the esterification reaction
is run at high pH. The carboxylic acid or corresponding carboxylate
may then react with another carboxylic acid chloride to yield an
anhydride linkage.
Anhydride linkages may be detected by means known to those skilled
in the art such as by .sup.13C nuclear magnetic resonance
spectroscopy (NMR). For example, resorcinol arylate polyesters
comprising dicarboxylic acid residues derived from a mixture of
iso- and terephthalic acids typically show .sup.13C NMR resonances
attributed to anhydride at 161.0 and 161.1 ppm (in
deuterochloroform relative to tetramethylsilane), as well as
resonances for the polymer carboxylic acid and hydroxyl end-groups.
After thermal processing (for example, extrusion and/or molding),
the polymer molecular weight decreases, and the anhydride
resonances typically decrease, while those of the acid and hydroxyl
end-groups typically increase.
Anhydride linkages in polymers comprising resorcinol arylate
polyester chain members may also be detected by reaction of polymer
with a nucleophile, such as a secondary amine. For example,
resorcinol arylate polyesters comprising dicarboxylic acid residues
derived from a mixture of iso- and terephthalic acids can be
dissolved in a convenient solvent, such as dichloromethane, and
treated with a secondary amine, such as dibutylamine or
diisobutylamine, for several minutes at ambient temperature.
Comparison of the starting polymer molecular weight to that after
amine treatment typically shows a decrease in molecular weight
which can be correlated with the corresponding decrease observed
under typical thermal processing conditions. Although the invention
is not meant to be limited by theory, it is believed that
nucleophiles, such as secondary amine and phenolic, attack
anhydride linkages (as opposed to ester linkages) selectively under
the reaction conditions. The decrease in molecular weight upon
reaction with amine nucleophile is therefore an indication of the
presence of anhydride functionality in the polymer.
In one of its aspects the present invention provides an interfacial
method for preparing polymers comprising resorcinol arylate
polyester chain members substantially free of anhydride linkages,
said method comprising a first step of combining at least one
resorcinol moiety and at least one catalyst in a mixture of water
and at least one organic solvent substantially immiscible with
water. Suitable resorcinol moieties comprise units of Formula V:
##STR00005## wherein R is at least one of C.sub.1-12 alkyl or
halogen, and n is 0-3. Alkyl groups, if present, are preferably
straight-chain or branched alkyl groups, and are most often located
in the ortho position to both oxygen atoms although other ring
locations are contemplated. Suitable C.sub.1-12 alkyl groups
include methyl, ethyl, n-propyl, isopropyl, butyl, iso-butyl,
t-butyl, nonyl, decyl, and aryl-substituted alkyl, including
benzyl, with methyl being particularly preferred. Suitable halogen
groups are bromo, chloro, and fluoro. The value for n may be 0-3,
preferably 0-2, and more preferably 0-1. A preferred resorcinol
moiety is 2-methylresorcinol. The most preferred resorcinol moiety
is an unsubstituted resorcinol moiety in which n is zero.
The method further comprises combining at least one catalyst with
the reaction mixture. Said catalyst may be present at a total level
of 0.1 to 10 mole %, and preferably 0.2 to 6 mole % based on total
molar amount of acid chloride groups. Suitable catalysts comprise
tertiary amines, quaternary ammonium salts, quaternary phosphonium
salts, hexaalkylguanidinium salts, and mixtures thereof. Suitable
tertiary amines include triethylamine, dimethylbutylamine,
diisopropylethylamine, 2,2,6,6-tetramethylpiperidine, and mixtures
thereof. Other contemplated tertiary amines include
N--C.sub.1-C.sub.6-alkyl-pyrrolidines, such as N-ethylpyrrolidine,
N--C.sub.1-C.sub.6-piperidines, such as N-ethylpiperidine,
N-methylpiperidine, and N-isopropylpiperidine,
N--C.sub.1-C.sub.6-morpholines, such as N-ethylmorpholine and
N-isopropyl-morpholine, N--C.sub.1-C.sub.6-dihydroindoles,
N--C.sub.1-C.sub.6-dihydroisoindoles,
N--C.sub.1-C.sub.6-tetrahydroquinolines,
N--C.sub.1-C.sub.6-tetrahydroisoquinolines,
N--C.sub.1-C.sub.6-benzo-morpholines, 1-azabicyclo-[3.3.0]-octane,
quinuclidine, N-C.sub.1-C.sub.6-alkyl-2-azabicyclo-[2.2.1]-octanes,
N--C.sub.1-C.sub.6-alkyl-2-azabicyclo-[3.3.1]-nonanes, and
N--C.sub.1-C.sub.6-alkyl-3-azabicyclo-[3.3.1]-nonanes, N,N,N',
N'-tetraalkylalkylenediamines, including
N,N,N',N'-tetraethyl-1,6-hexanediamine. Particularly preferred
tertiary amines are triethylamine and N-ethylpiperidine.
When the catalyst consists of at least one tertiary amine alone,
then said catalyst may be present at a total level of 0.1 to 10
mole %, preferably 0.2 to 6 mole %, more preferably 1 to 4 mole %,
and most preferably 2.5 to 4 mole % based on total molar amount of
acid chloride groups. In one embodiment of the invention all of the
at least one tertiary amine is present at the beginning of the
reaction before addition of dicarboxylic acid dichloride to
resorcinol moiety. In another embodiment a portion of any tertiary
amine is present at the beginning of the reaction and a portion is
added following or during addition of dicarboxylic acid dichloride
to resorcinol moiety. In this latter embodiment the amount of any
tertiary amine initially present with resorcinol moiety may range
from about 0.005 wt. % to about 10 wt. %, preferably from about
0.01 to about 1 wt. %, and more preferably from about 0.02 to about
0.3 wt. % based on total amine.
Suitable quaternary ammonium salts, quaternary phosphonium salts,
and hexaalkylguanidinium salts include halide salts such as
tetraethylammonium bromide, tetraethylammonium chloride,
tetrapropylammonium bromide, tetrapropylammonium chloride,
tetrabutylammonium bromide, tetrabutylammonium chloride,
methyltributylammonium chloride, benzyltributylammonium chloride,
benzyltriethylammonium chloride, benzyltrimethylammonium chloride,
trioctylmethylammonium chloride, cetyldimethylbenzylammonium
chloride, octyltriethylammonium bromide, decyltriethylammonium
bromide, lauryltriethylammonium bromide, cetyltrimethylammonium
bromide, cetyltriethylammonium bromide, N-laurylpyridinium
chloride, N-laurylpyridinium bromide, N-heptylpyridinium bromide,
tricaprylylmethylammonium chloride (sometimes known as ALIQUAT
336), methyltri-C.sub.8-C.sub.10-alkyl-ammonium chloride (sometimes
known as ADOGEN 464), N,N,N',N',N'-pentaalkyl-alpha,
omega-amineammonium salts such as disclosed in U.S. Pat. No.
5,821,322; tetrabutylphosphonium bromide,
benzyltriphenylphosphonium chloride, triethyloctadecylphosphonium
bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium
bromide, trioctylethylphosphonium bromide, cetyltriethylphosphonium
bromide, hexaalkylguanidinium halides, hexaethylguanidinium
chloride, and the like, and mixtures thereof.
Organic solvents substantially immiscible with water include those
which are less than about 5 wt. %, and preferably less than about 2
wt. % soluble in water under the reaction conditions. Suitable
organic solvents include dichloromethane, trichloroethylene,
tetrachloroethane, chloroform, 1,2-dichloroethane, toluene, xylene,
trimethylbenzene, chlorobenzene, o-dichlorobenzene, and mixtures
thereof. An especially preferred solvent is dichloromethane.
Suitable dicarboxylic acid dichlorides comprise aromatic
dicarboxylic acid dichlorides derived from monocyclic moieties,
preferably isophthaloyl dichloride, terephthaloyl dichloride, or
mixtures of isophthaloyl and terephthaloyl dichlorides, or from
polycyclic moieties, including diphenyl dicarboxylic acid
dichloride, diphenylether dicarboxylic acid dichloride, and
naphthalenedicarboxylic acid dichloride, preferably
naphthalene-2,6-dicarboxylic acid dichloride; or from mixtures of
monocyclic and polycyclic aromatic dicarboxylic acid dichlorides.
Preferably, the dicarboxylic acid dichloride comprises mixtures of
isophthaloyl and/or terephthaloyl dichlorides as typically
illustrated in Formula VI. ##STR00006## Either or both of
isophthaloyl and terephthaloyl dichlorides may be present. In
especially preferred embodiments the dicarboxylic acid dichlorides
comprise mixtures of isophthaloyl and terephthaloyl dichloride in a
molar ratio of isophthaloyl to terephthaloyl of about 0.25-4.0:1,
preferably about 0.4-2.5:1, and more preferably about
0.67-1.5:1.
The pH of the reaction mixture is maintained between about 3 and
about 8.5, and preferably between about 5 and about 8, throughout
addition of the at least one dicarboxylic acid dichloride to the at
least one resorcinol moiety. Suitable reagents to maintain the pH
include alkali metal hydroxides, alkaline earth hydroxides, and
alkaline earth oxides. Preferred reagents are potassium hydroxide
and sodium hydroxide. A particularly preferred reagent is sodium
hydroxide. The reagent to maintain pH may be included in the
reaction mixture in any convenient form. Preferably, said reagent
is added to the reaction mixture as an aqueous solution
simultaneously with the at least one dicarboxylic acid
dichloride.
The temperature of the reaction mixture may be any convenient
temperature that provides a rapid reaction rate and a resorcinol
arylate-containing polymer substantially free of anhydride
linkages. Convenient temperatures include those from about
-20.degree. C. to the boiling point of the water-organic solvent
mixture under the reaction conditions. In a preferred embodiment
the reaction is performed at the boiling point of the organic
solvent in the water-organic solvent mixture. In an especially
preferred embodiment the reaction is performed at the boiling point
of dichloromethane.
The total molar amount of acid chloride groups added to the
reaction mixture is stoichiometrically deficient relative to the
total molar amount of phenolic groups. Said stoichiometric ratio is
desirable so that hydrolysis of acid chloride groups is minimized,
and so that nucleophiles such as phenolic and/or phenoxide may be
present to destroy any adventitious anhydride linkages, should any
form under the reaction conditions. The total molar amount of acid
chloride groups includes the at least one dicarboxylic acid
dichloride, and any mono-carboxylic acid chloride chain-stoppers
and any tri- or tetra-carboxylic acid tri- or tetra-chloride
branching agents which may be used. The total molar amount of
phenolic groups includes resorcinol moieties, and any mono-phenolic
chain-stoppers and any tri- or tetra-phenolic branching agents
which may be used. The stoichiometric ratio of total phenolic
groups to total acid chloride groups is preferably about 1.5-1.01:1
and more preferably about 1.2-1.02:1.
The presence or absence of adventitious anhydride linkages
following complete addition of the at least one dicarboxylic acid
dichloride to the at least one resorcinol moiety will typically
depend upon the exact stoichiometric ratio of reactants and the
amount of catalyst present, as well as other variables. For
example, if a sufficient molar excess of total phenolic groups is
present, anhydride linkages are often found to be absent. Often a
molar excess of at least about 1% and preferably at least about 3%
of total amount of phenolic groups over total amount of said
chloride groups may suffice to eliminate anhydride linkages under
the reaction conditions. When anhydride linkages may be present, it
is often desirable that the final pH be greater than 7 so that
nucleophiles such as phenolic, phenoxide and/or hydroxide may be
present to destroy any adventitious anhydride linkages. Therefore,
in one of its aspects the method of the invention may further
comprise the step of adjusting the pH of the reaction mixture to
between 7 and 12, preferably to between 8 and 12, and more
preferably to between 8.5 and 12, following complete addition of
the at least one dicarboxylic acid dichloride to the at least one
resorcinol moiety. The pH may be adjusted by any convenient method,
preferably using an aqueous base such as aqueous sodium
hydroxide.
Provided the final pH of the reaction mixture is greater than 7,
the method of the invention may further comprise the step of
stirring the reaction mixture for a time sufficient to destroy
completely any adventitious anhydride linkages, should any be
present. The necessary stirring time will depend upon reactor
configuration, stirrer geometry, stirring rate, temperature, total
solvent volume, organic solvent volume, anhydride concentration,
pH, and other factors. In some instances the necessary stirring
time is essentially instantaneous, for example within seconds of pH
adjustment to above 7, assuming any adventitious anhydride linkages
were present to begin with. For typical laboratory scale reaction
equipment a stirring time of at least about 3 minutes, and
preferably at least about 5 minutes may be required. By this
process nucleophiles, such as phenolic, phenoxide and/or hydroxide,
may have time to destroy completely any adventitious anhydride
linkages, should any be present.
At least one chain-stopper (also referred to sometimes hereinafter
as capping agent) may also be present in the method and
compositions of the invention. A purpose of adding at least one
chain-stopper is to limit the molecular weight of polymer
comprising resorcinol arylate polyester chain members, thus
providing polymer with controlled molecular weight and favorable
processability. Typically, at least one chain-stopper is added when
the resorcinol arylate-containing polymer is not required to have
reactive end-groups for further application. In the absence of
chain-stopper resorcinol arylate-containing polymer may be either
used in solution or recovered from solution for subsequent use such
as in copolymer formation which may require the presence of
reactive end-groups, typically hydroxy, on the resorcinol-arylate
polyester segments. A chain-stopper may be at least one of
mono-phenolic compounds, mono-carboxylic acid chlorides, and/or
mono-chloroformates. Typically, the at least one chain-stopper may
be present in quantities of 0.05 to 10 mole %, based on resorcinol
moieties in the case of mono-phenolic compounds and based on acid
dichlorides in the case mono-carboxylic acid chlorides and/or
mono-chloroformates.
Suitable mono-phenolic compounds include monocyclic phenols, such
as phenol, C.sub.1-C.sub.22 alkyl-substituted phenols,
p-cumyl-phenol, p-tertiary-butyl phenol, hydroxy diphenyl;
monoethers of diphenols, such as p-methoxyphenol. Alkyl-substituted
phenols include those with branched chain alkyl substituents having
8 to 9 carbon atoms, preferably in which about 47 to 89% of the
hydrogen atoms are part of methyl groups as described in U.S. Pat.
No. 4,334,053. For some embodiments the use of a mono-phenolic UV
screener as capping agent is preferred. Such compounds include
4-substituted-2-hydroxybenzophenones and their derivatives, aryl
salicylates, monoesters of diphenols, such as resorcinol
monobenzoate, 2-(2-hydroxyaryl)-benzotriazoles and their
derivatives, 2-(2-hydroxyaryl)-1,3-5-triazines and their
derivatives, and like compounds. Especially preferred mono-phenolic
chain-stoppers are phenol, p-cumylphenol, and resorcinol
monobenzoate.
Suitable mono-carboxylic acid chlorides include monocyclic,
mono-carboxylic acid chlorides, such as benzoyl chloride,
C.sub.1-C.sub.22 alkyl-substituted benzoyl chloride, toluoyl
chloride, halogen-substituted benzoyl chloride, bromobenzoyl
chloride, cinnamoyl chloride, 4-nadimidobenzoyl chloride, and
mixtures thereof; polycyclic, mono-carboxylic acid chlorides, such
as trimellitic anhydride chloride, and naphthoyl chloride; and
mixtures of monocyclic and polycyclic mono-carboxylic acid
chlorides. The chlorides of aliphatic monocarboxylic ac ids with up
to 22 carbon atoms are also suitable. Functionalized chlorides of
aliphatic monocarboxylic acids, such as acryloyl chloride and
methacryoyl chloride, are also suitable. Suitable
mono-chloroformates include monocyclic, mono-chloroformates, such
as phenyl chloroformate, alkyl-substituted phenyl chloroformate,
p-cumyl phenyl chloroformate, toluene chloroformate, and mixtures
thereof.
A chain-stopper can be combined together with the resorcinol
moieties, can be contained in the solution of dicarboxylic acid
dichlorides, or can be added to the reaction mixture after
production of a precondensate. If monocarboxylic acid chlorides
and/or mono-chloroformates are used as chain-stoppers, they are
preferably introduced together with dicarboxylic acid dichlorides.
These chain-stoppers can also be added to the reaction mixture at a
moment when the chlorides of dicarboxylic acid have already reacted
substantially or to completion. If phenolic compounds are used as
chain-stoppers, they can be added to the reaction mixture during
the reaction, or, more preferably, before the beginning of the
reaction between resorcinol moiety and acid chloride moiety. When
hydroxy-terminated resorcinol arylate-containing precondensate or
oligomers are prepared, then chain-stopper may be absent or only
present in small amounts to aid control of oligomer molecular
weight.
In another embodiment the invention may encompass the inclusion of
at least one branching agent such as a trifunctional or higher
functional carboxylic acid chloride and/or trifunctional or higher
functional phenol. Such branching agents, if included, can
preferably be used in quantities of 0.005 to 1 mole %, based on
dicarboxylic acid dichlorides or resorcinol moieties used,
respectively. Suitable branching agents include, for example,
trifunctional or higher carboxylic acid chlorides, such as trimesic
acid trichloride, cyanuric acid trichloride, 3,3',4,4'-benzophenone
tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalene
tetracarboxylic acid tetrachloride or pyromellitic acid
tetrachloride, and trifunctional or higher phenols, such as
phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-2-heptene,
4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane,
1,3,5-tri-(4-hydroxyphenyl)-benzene,
1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenyl
methane, 2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane,
2,4-bis-(4-hydroxyphenylisopropyl)-phenol,
tetra-(4-hydroxyphenyl)-methane,
2,6-bis-(2-hydroxy-5-methylbenzyl)-4-methyl phenol,
2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane,
tetra-(4-[4-hydroxyphenylisopropyl]-phenoxy)-methane,
1,4-bis-[(4,4-dihydroxytriphenyl)methyl]-benzene. Phenolic
branching agents may be introduced first with the resorcinol
moieties whilst acid chloride branching agents may be introduced
together with acid dichlorides.
For some applications such as for copolymer formation the
resorcinol arylate-containing polymer may remain in solution for
subsequent process steps. In other instances such as in the
production of resorcinol arylate polyester the polymer will
normally be isolated from solution. Therefore, in another
embodiment of the invention the resorcinol arylate-containing
polymer is recovered from the reaction mixture. Recovery methods
are well known to those skilled in the art and may include such
steps as acidification of the mixture, for example with phosphorous
acid; subjecting the mixture to liquid-liquid phase separation;
washing the organic phase with water and/or a dilute acid such as
hydrochloric acid or phosphoric acid; precipitating by usual
methods such as through treatment with water or anti-solvent
precipitation with, for example, methanol, ethanol, and/or
isopropanol; isolating the resulting precipitates; and drying to
remove residual solvents.
If desired, the resorcinol arylate polymers of the invention may be
made by the present method further comprising the addition of a
reducing agent. Suitable reducing agents include, for example,
sodium sulfite, sodium gluconate, or a borohydride, such as sodium
borohydride. When present, any reducing agents are typically used
in quantities of from 0.25 to 2 mole %, based on moles of
resorcinol moiety.
In one of its embodiments the invention comprises thermally stable
resorcinol arylate polyesters made by the present method and
substantially free of anhydride linkages linking at least two mers
of the polyester chain: In a particular embodiment said polyesters
comprise dicarboxylic acid residues derived from a mixture of iso-
and terephthalic acids as illustrated in Formula VII: ##STR00007##
wherein R is at least one of C.sub.1-12 alkyl or halogen, n is 0-3,
and m is at least about 8. Preferably, n is zero and m is between
about 10 and about 300. The molar ratio of isophthalate to
terephthalate is about 0.25-4.0:1, preferably about 0.4-2.5:1, and
more preferably about 0.67-1.5:1. Substantially free of anhydride
linkages means that said polyesters show decrease in molecular
weight of less than 30% and preferably less than 10% upon heating
said polymer at a temperature of about 280-290.degree. C. for five
minutes.
The present invention also encompasses thermally stable copolymers
containing segments comprising resorcinol arylate polyester chain
members made by the present method and substantially free of
anhydride linkages linking at least two mers of the copolymer
chain. Thus, in another of its embodiments the present invention
comprises thermally stable copolyesters comprising resorcinol
arylate polyester chain members in combination with dicarboxylic
acid or diol alkylene chain members (so-called "soft-block"
segments), said copolyesters being substantially free of anhydride
linkages in the polyester segments. Substantially free of anhydride
linkages means that the copolyesters show decrease in molecular
weight of less than 10% and preferably less than 5% upon heating
said copolyester at a temperature of about 280-290.degree. C. for
five minutes. Related copolyesters containing soft-block segments
are disclosed in U.S. Pat. No. 5,916,997, the disclosure of which
is incorporated by reference herein.
The term soft-block as used herein, indicates that some segments of
the polymers are made from non-aromatic monomer units. Such
non-aromatic monomer units are generally aliphatic and are known to
impart flexibility to the soft-block-containing polymers. The
copolymers include those comprising structural units of Formulas I,
VIII, and IX. ##STR00008## wherein R and n are as previously
defined, Z is a divalent aromatic radical, R.sup.2 is a C.sub.3-20
straight chain alkylene, C.sub.3-10 branched alkylene, or
C.sub.4-10 cyclo- or bicycloalkylene group, and R.sup.3 and R.sup.4
each independently represent ##STR00009## wherein Formula IX
contributes from about 1 to about 45 mole percent to the ester
linkages of the polyester. Additional embodiments of the present
invention provide a composition wherein Formula IX contributes from
about 5 to about 40 mole percent to the ester linkages of the
polyester, with about 5 to about 20 mole percent being particularly
preferred. Another embodiment provides a composition where R.sup.2
represents C.sub.3-14 straight chain alkylene, or C.sub.5-6
cycloalkylene, with a preferred composition being one wherein
R.sup.2 represents C.sub.3-10 straight-chain alkylene or
C.sub.6-cycloalkylene. Formula VIII represents an aromatic
dicarboxylic acid residue. The divalent aromatic radical Z in
Formula VIII may be derived from at least one of the suitable
dicarboxylic acid residues as defined hereinabove, and preferably
at least one of 1,3-phenylene, 1,4-phenylene, or 2,6-naphthylene.
In more preferred embodiments Z comprises at least about 40 mole
percent 1,3-phenylene. In preferred embodiments of copolyesters
containing soft-block chain members n in Formula I is zero.
Preferred copolyesters containing resorcinol arylate chain members
are those comprising from about 1 to about 45 mole % sebacate or
cyclohexane 1,4-dicarboxylate units. A particularly preferred
copolyester containing resorcinol arylate chain members is one
comprising resorcinol isophthalate and resorcinol sebacate units in
molar ratio between 8.5:1.5 and 9.5:0.5. In a preferred procedure
said preferred copolyester is prepared using sebacoyl chloride in
combination with isophthaloyl chloride.
In another of its embodiments the present invention comprises
thermally stable block copolyestercarbonates comprising resorcinol
arylate-containing block segments in combination with organic
carbonate block segments. The segments comprising resorcinol
arylate chain members in such copolymers are substantially free of
anhydride linkages. Substantially free of anhydride linkages means
that the copolyestercarbonates show decrease in molecular weight of
less than 10% and preferably less than 5% upon heating said
copolyestercarbonate at a temperature of about 280-290.degree. C.
for five minutes. Related block copolyestercarbonates are disclosed
in commonly owned co-pending application Ser. No. 09/181,902 (now
abandoned), the disclosure of which is incorporated by reference
herein.
The block copolyestercarbonates include those comprising
alternating arylate and organic carbonate blocks, typically as
illustrated in Formula X, wherein R and n are as previously
defined, and R.sub.5 is at least one divalent organic radical:
##STR00010##
The arylate blocks have a degree of polymerization (DP),
represented by m, of at least about 4, preferably at least about
10, more preferably at least about 20 and most preferably about
30-150. The DP of the organic carbonate blocks, represented by p,
is generally at least about 10, preferably at least about 20 and
most preferably about 50-200. The distribution of the blocks may be
such as to provide a copolymer having any desired weight proportion
of arylate blocks in relation to carbonate blocks. In general, the
content of arylate blocks is preferably about 10-95% by weight and
more preferably about 50-95% by weight.
Although a mixture of iso- and terephthalate is illustrated in
Formula X, the dicarboxylic acid residues in the arylate blocks may
be derived from any suitable dicarboxylic acid residue, as defined
hereinabove, or mixture of suitable dicarboxylic acid residues,
including those derived from aliphatic diacid dichlorides
(so-called "soft-block" segments). In preferred embodiments n is
zero and the arylate blocks comprise dicarboxylic acid residues
derived from a mixture of iso- and terephthalic acid residues,
wherein the molar ratio of isophthalate to terephthalate is about
0.25-4.0:1, preferably about 0.4-2.5:1, and more preferably about
0.67-1.5:1.
In the organic carbonate blocks, each R.sup.5 is independently a
divalent organic radical. Preferably, said radical comprises at
least one dihydroxy-substituted aromatic hydrocarbon, and at least
about 60 percent of the total number of R.sup.5 groups in the
polymer are aromatic organic radicals and the balance thereof are
aliphatic, alicyclic, or aromatic radicals. Suitable R.sup.5
radicals include m-phenylene, p-phenylene, 4,4'-biphenylene,
4,4'-bi(3,5-dimethyl)-phenylene, 2,2-bis (4-phenylene)propane,
6,6'-(3,3,3',3'-tetramethyl-1,1'-spirobi[1H-indan]) and similar
radicals such as those which correspond to the
dihydroxy-substituted aromatic hydrocarbons disclosed by name or
formula (generic or specific) in U.S. Pat. No. 4,217,438, which is
incorporated herein by reference.
More preferably, each R.sup.5 is an aromatic organic radical and
still more preferably a radical of Formula XI:
--A.sup.1--Y--A.sup.2-- Formula XI wherein each A.sup.1 and A.sup.2
is a monocyclic divalent aryl radical and Y is a bridging radical
in which one or two carbon atoms separate A.sup.1 and A.sup.2. The
free valence bonds in Formula XI are usually in the meta or para
positions of A.sup.1 and A.sup.2 in relation to Y. Compounds in
which R.sup.5 has Formula XI are bisphenols, and for the sake of
brevity the term "bisphenol" is sometimes used herein to designate
the dihydroxy-substituted aromatic hydrocarbons. It should be
understood, however, that non-bisphenol compounds of this type may
also be employed as appropriate.
In Formula XI, A.sup.1 and A.sup.2 typically represent
unsubstituted phenylene or substituted derivatives thereof,
illustrative substituents (one or more) being alkyl, alkenyl, and
halogen (particularly bromine). Unsubstituted phenylene radicals
are preferred. Both A.sup.1 and A.sup.2 are preferably p-phenylene,
although both may be o- or m-phenylene or one o- or m-phenylene and
the other p-phenylene.
The bridging radical, Y, is one in which one or two atoms, separate
A.sup.1 from A.sup.2. The preferred embodiment is one in which one
atom separates A.sup.1 from A.sup.2. Illustrative radicals of this
type are --O--, --S--, --SO-- or --SO.sub.2--, methylene,
cyclohexyl methylene, 2-[2.2.1]-bicycloheptyl methylene, ethylene,
isopropylidene, neopentylidene, cyclohexylidine,
cyclopentadecylidene, cyclododecylidene, adamantylidene, and like
radicals.
Gem-alkylene (commonly known as "alkylidene") radicals are
preferred. Also included, however, are unsaturated radicals. For
reasons of availability and particular suitability for the purposes
of this invention, the preferred bisphenol is
2,2-bis(4-hydroxyphenyl)propane (bisphenol-A or BPA), in which Y is
isopropylidene and A.sup.1 and A.sup.2 are each p-phenylene.
Depending upon the molar excess of resorcinol moiety present in the
reaction mixture, R.sup.5 in the carbonate blocks may at least
partially comprise resorcinol moiety. In other words, in some
embodiments of the invention carbonate blocks of Formula X may
comprise a resorcinol moiety in combination with at least one other
dihydroxy-substituted aromatic hydrocarbon.
Diblock, triblock, and multiblock copolyestercarbonates are
encompassed in the present invention. The chemical linkages between
blocks comprising resorcinol arylate chain members and blocks
comprising organic carbonate chain members may comprise at least
one of (a) an ester linkage between a suitable dicarboxylic acid
residue of an arylate moiety and an --O--R.sup.5--O-- moiety of an
organic carbonate moiety, for example as typically illustrated in
Formula XII, wherein R.sup.5 is as previously defined: ##STR00011##
and (b) a carbonate linkage between a diphenol residue of a
resorcinol arylate moiety and a --(C.dbd.O)--O-- moiety of an
organic carbonate moiety as shown in Formula XIII, wherein R and n
are as previously defined: ##STR00012##
The presence of a significant proportion of ester linkages of the
type (a) may result in undesirable color formation in the
copolyestercarbonates. Although the invention is not limited by
theory, it is believed that color may arise, for example, when
R.sup.5 in Formula XII is bisphenol A and the moiety of Formula XII
undergoes Fries rearrangement during subsequent processing and/or
light-exposure. In a preferred embodiment the copolyestercarbonate
is substantially comprised of a diblock copolymer with a carbonate
linkage between resorcinol arylate block and an organic carbonate
block. In a more preferred embodiment the copolyestercarbonate is
substantially comprised of a triblock carbonate-ester-carbonate
copolymer with carbonate linkages between the resorcinol arylate
block and organic carbonate end-blocks.
Copolyestercarbonates with at least one carbonate linkage between a
thermally stable resorcinol arylate block and an organic carbonate
block are typically prepared from resorcinol arylate-containing
oligomers prepared by the method of the invention and containing at
least one and preferably two hydroxy-terminal sites. Said oligomers
typically have weight average molecular weight of about 10,000 to
about 40,000, and more preferably about 15,000 to about 30,000.
Thermally stable copolyestercarbonates may be prepared by reacting
said resorcinol arylate-containing oligomers with phosgene, at
least one chain-stopper, and at least one dihydroxy-substituted
aromatic hydrocarbon in the presence of a catalyst such as a
tertiary amine.
It is believed that the weatherability and certain other beneficial
properties of the polymers comprising resorcinol arylate polyester
chain members of the invention are attributable, at least in part,
to the occurrence of thermally or photochemically induced Fries
rearrangement of arylate blocks to yield o-hydroxybenzophenone
moieties or analogs thereof which serve as stabilizers to UV
radiation. More particularly, at least a portion of resorcinol
arylate polyester chain members can rearrange to yield chain
members with at least one hydroxy group ortho to at least one
ketone group. Such rearranged chain members are typically
o-hydroxybenzophenone-type chain members comprising one or more of
the FOLLOWING structural moieties: ##STR00013## wherein R and n are
as previously defined. The o-hydroxy-benzophenone-type chain
members resulting from rearrangement of resorcinol arylate chain
members can be present in resorcinol arylate polyesters and in
resorcinol arylate polyester-containing copolymers, including
resorcinol arylate-containing copolyestercarbonates and resorcinol
arylate-containing copolyesters containing soft-blocks. It is also
contemplated to introduce moieties of the types illustrated in
Formulas XIV, XV, and XVI via synthesis and polymerization of
appropriate monomers in both homopolymers and copolymers by the
method of the present invention. In one embodiment the present
invention provides thermally stable polyesters,
copolyestercarbonates, and copolyesters comprising structural units
represented by Formulas III and XIV, wherein the molar ratio of
structural units represented by Formula III to structural units
represented by Formula XIV ranges from about 99:1 to about 1:1, and
preferably from about 99:1 to about 80:20.
The polymers and copolymers comprising thermally stable resorcinol
arylate polyester chain members may also be employed as
weatherability-improving additives in blends with at least one
other polymer, especially polycarbonates (hereinafter sometimes
designated "PC"), polyesters, polyetherimides, polyphenylene
ethers, and addition polymers. Related blends are disclosed in
commonly owned, co-pending application Ser. No. 09/152,877, the
disclosure of which is incorporated by reference herein.
The polycarbonates in the blend compositions of the invention are,
for the most part, similar in molecular structure to the carbonate
blocks of the block copolyestercarbonate as described hereinabove,
with bisphenol-A homo- and copolycarbonates generally being
preferred. Polyesters are illustrated by poly(alkylene
dicarboxylates), especially poly (ethylene terephthalate)
(hereinafter sometimes designated "PET"), poly(1,4-butylene
terephthalate) (hereinafter sometimes designated "PBT"),
poly(trimethylene terephthalate) (hereinafter sometimes designated
"PTT"), poly(ethylene naphthalate) (hereinafter sometimes
designated "PEN"), poly(butylene naphthalate) (hereinafter
sometimes designated "PBN"), poly(cyclohexanedimethanol
terephthalate), poly(cyclohexanedimethanol-co-ethylene
terephthalate) (hereinafter sometimes designated "PETG"), and
poly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate)
(hereinafter sometimes designated "PCCD"), and especially
poly(alkylene arenedioates), with poly(ethylene terephthalate) and
poly(1,4-butylene terephthalate) being preferred.
Copolyestercarbonates may also be used in blends with polymers
comprising resorcinol arylate polyester chain members. Such
copolymers comprise, in addition to the organic carbonate units,
ester units such as isophthalate and/or terephthalate. The
copolyester-carbonates which find use in the instant invention and
the methods for their preparation are well known in the art as
disclosed in, for example, U.S. Pat. Nos. 3,030,331; 3,169,121;
3,207,814; 4,194,038; 4,156,069; 4,238,596; 4,238,597; 4,487,896;
and 4,506,065.
Suitable addition polymers include homopolymers and copolymers,
especially homopolymers of alkenylaromatic compounds, such as
polystyrene, including syndiotactic polystyrene, and copolymers of
alkenylaromatic compounds with ethylenically unsaturated nitriles,
such as acrylonitrile and methacrylonitrile; dienes, such as
butadiene and isoprene; and/or acrylic monomers, such as ethyl
arcylate. These latter copolymers include the ABS
(acrylonitrile-butadiene-styrene) and ASA
(acrylonitrile-styrene-alkyl acrylate) copolymers.
In another embodiment the invention encompasses blends of polymers
and/or copolymers comprising thermally stable resorcinol arylate
polyester chain members with at least two other polymers. Said at
least two other polymers may comprise miscible, immiscible, and
compatibilized blends including, but not limited to, PC/ABS,
PC/ASA, PC/PBT, PC/PET, PC/polyetherimide,
polyester/polyetherimide, polyphenylene ether/polystyrene,
polyphenylene ether/polyamide, and polyphenylene
ether/polyester.
The blend composition of the invention may be prepared by such
conventional operations as solvent blending and melt blending. A
particularly preferred method for blend preparation is melt
blending such as by extrusion. The blends may additionally contain
art-recognized additives including pigments, dyes, impact
modifiers, UV screeners, flame retardants, fillers, stabilizers,
flow aids, ester interchange inhibitors, and mold release agents.
It is intended that the blend compositions include simple physical
blends and any reaction products thereof, as illustrated, for
example, by polyester-polycarbonate transesterification
products.
Proportions of the polymers comprising resorcinol arylate polyester
chain members in such blends are determined chiefly by the
resulting proportions of arylate blocks, which most often comprise
the active weatherability-improving entities, typical proportions
providing about 10-50% by weight of arylate blocks in the blend. In
blends where some degree of incompatibility may exist between the
polymers comprising resorcinol arylate polyester chain members of
the invention and the polycarbonates, polyesters, or addition
polymers with which they may be combined, said blends are sometimes
not fully transparent. However, transparent blends may often be
prepared by adjusting the length of the arylate blocks in the
polymers comprising resorcinol arylate polyester chain members. The
other properties of said blends are generally excellent.
Compositions comprising resorcinol arylate polyester chain members
made by the method of the invention typically have significantly
lower color, both before and after thermal processing, than related
compositions made by melt methods, interfacial methods, and
solution methods of the prior art. In particular, melt methods
typically provide resorcinol arylate polyester with tan to dark
brown color while the present interfacial method provides very
lightly colored or essentially colorless polyester. The present
compositions may be used in various applications, especially those
involving outdoor use and storage, and hence requiring resistance
to weathering. Their light transmitting properties are often
similar to those of polycarbonates. Thus, they are often
substantially transparent and colorless, and may often be employed
as substitutes for polycarbonates in the fabrication of transparent
sheet material when improved weatherability is mandated.
In another embodiment the present invention comprises multilayer
articles comprising a substrate layer comprising at least one
thermoplastic polymer, thermoset polymer, cellulosic material,
glass, ceramic, or metal, and at least one coating layer thereon,
said coating layer comprising a thermally stable polymer comprising
resorcinol arylate polyester chain members substantially free of
anhydride linkages linking at least two mers of the polymer chain.
Optionally, the multilayer articles may further comprise an
interlayer, for example an adhesive interlayer, between any
substrate layer and any thermally stable polymer coating layer.
Multilayer articles of the invention include, but are not limited
to, those which comprise a substrate layer and a coating layer of
said thermally stable polymer; those which comprise a substrate
layer with a coating layer of said thermally stable polymer on each
side of said substrate layer; and those which comprise a substrate
layer and at least one coating layer of said thermally stable
polymer with at least one interlayer between a substrate layer and
a coating layer. Any interlayer may be transparent and/or may
contain an additive, for example a colorant or decorative material
such as metal flake. If desired, an overlayer may be included over
the coating layer of thermally stable polymer, for example to
provide abrasion or scratch resistance. The substrate layer,
coating layer of thermally stable polymer, and any interlayers or
overcoating layers are preferably in contiguous superposed contact
with one another.
Within the context of the present invention it should be understood
that any coating layer comprising a thermally stable polymer
comprising resorcinol arylate polyester chain members will also
include polymer comprising o-hydroxy-benzophenone or analogous
chain members resulting from Fries rearrangement of said resorcinol
arylate chain members, for example after exposure of said coating
layer to UV-light. Typically, a preponderance of polymer comprising
o-hydroxy-benzophenone or analogous chain members will be on that
side or sides of said coating layer exposed to UV-light and will
overlay in a contiguous superposed layer or layers that polymer
comprising unrearranged resorcinol arylate chain members. If it is
worn away or otherwise removed, polymer comprising
o-hydroxybenzophenone or analogous chain members is capable of
regenerating or renewing itself from the resorcinol
arylate-containing layer or layers, thus providing continuous
protection for any UV-light sensitive layers.
The multilayer articles typically have outstanding initial gloss,
improved initial color, weatherability, impact strength, and
resistance to organic solvents encountered in their final
applications. Said articles may also be recyclable by reason of the
compatibility of the discrete layers therein.
The material of the substrate layer in the articles of this
invention may be at least one thermoplastic polymer, whether
addition or condensation prepared. Condensation polymers include,
but are not limited to, polycarbonates, particularly aromatic
polycarbonates, polyphenylene ethers, polyetherimides, polyesters
(other than those employed for the coating layer, as defined
hereinafter), and polyamides. Polycarbonate and polyesters are
frequently preferred.
Suitable polycarbonates include homopolycarbonates comprising
structural units of the type described for the organic carbonate
blocks in the copolyestercarbonates of the invention. The most
preferred polycarbonates are bisphenol A homo- and
copolycarbonates. Preferably, the weight average molecular weight
of the initial polycarbonate ranges from about 5,000 to about
100,000; more preferably, from about 25,000 to about 65,000.
The polycarbonate substrate may also be a copolyestercarbonate
(other than that copolyestercarbonate employed for the coating
layer as defined hereinafter). Such copolymers typically comprise,
in addition to the organic carbonate units, ester units such as
isophthalate and/or terephthalate. The copolyestercarbonates which
find use in the instant invention and the methods for their
preparation are well known in the art as disclosed in, for example,
U.S. Pat. Nos. 3,030,331; 3,169,121; 3,207,814; 4,194,038;
4,156,069; 4,238,596; 4,238,597; 4,487,896; and 4,506,065.
Polyester substrates include, but are not limited to, poly
(ethylene terephthalate), poly(1,4-butylene terephthalate),
poly(trimethylene terephthalate), poly(ethylene naphthalate),
poly(butylene naphthalate), poly (cyclohexanedimethanol
terephthalate), poly (cyclohexanedimethanol-co-ethylene
terephthalate), and
poly(1,4-cyclohexanedimethyl-1,4-cyclohexanedicarboxylate).
Suitable addition polymer substrates include homo- and copolymeric
aliphatic olefin and functionalized olefin polymers such as
polyethylene, polypropylene, poly(vinyl chloride), poly(vinyl
chloride-co-vinylidene chloride), poly (vinyl fluoride),
poly(vinylidene fluoride), poly(vinyl acetate), poly(vinyl
alcohol), poly(vinyl butyral), poly (acrylonitrile), acrylic
polymers such as those of (meth) acrylamides or of alkyl
(meth)acrylates such as poly(methyl methacrylate) ("PMMA"), and
polymers of alkenylaromatic compounds such as polystyrenes,
including syndiotactic polystyrene. The preferred addition polymers
for many purposes are polystyrenes and especially the so-called ABS
and ASA copolymers, which may contain thermoplastic,
non-elastomeric styrene-acrylontrile side chains grafted on an
elastomeric base polymer of butadiene and alkyl acrylate,
respectively.
Blends of any of the foregoing polymers may also be employed as
substrates. Typical blends include, but are not limited to, those
comprising PC/ABS, PC/ASA, PC/PBT, PC/PET, PC/polyetherimide,
PC/polysulfone, polyester/polyetherimide, PMMA/acrylic rubber,
polyphenylene ether-polystyrene, polyphenylene ether-polyamide or
polyphenylene ether-polyester. Although the substrate layer may
incorporate other thermoplastic polymers, the above-described
polycarbonates and/or addition polymers still more preferably
constitute the major proportion thereof.
The substrate layer in the multilayer articles of this invention
may also comprise at least one of any thermoset polymer. Suitable
thermoset polymer substrates include, but are not limited to, those
derived from epoxys, cyanate esters, unsaturated polyesters,
diallylphthalate, acrylics, alkyds, phenol-formaldehyde, novolacs,
resoles, bismaleimides, PMR resins, melamine-formaldehyde,
urea-formaldehyde, benzocyclobutanes, hydroxymethylfurans, and
isocyanates. In one embodiment of the invention the thermoset
polymer substrate further comprises at least one thermoplastic
polymer, such as, but not limited to, polyphenylene ether,
polyphenylene sulfide, polysulfone, polyetherimide, or polyester.
Said thermoplastic polymer is typically combined with thermoset
monomer mixture before curing of said thermoset.
In one embodiment of the invention a thermoplastic or thermoset
substrate layer also incorporates at least one filler and/or
pigment. Illustrative extending and reinforcing fillers, and
pigments include silicates, zeolites, titanium dioxide, stone
powder, glass fibers or spheres, carbon fibers, carbon black,
graphite, calcium carbonate, talc, mica, lithopone, zinc oxide,
zirconium silicate, iron oxides, diatomaceous earth, calcium
carbonate, magnesium oxide, chromic oxide, zirconium oxide,
aluminum oxide, crushed quartz, calcined clay, talc, kaolin,
asbestos, cellulose, wood flour, cork, cotton and synthetic textile
fibers, especially reinforcing fillers such as glass fibers and
carbon fibers, as well as colorants such as metal flakes, glass
flakes and beads, ceramic particles, other polymer particles, dyes
and pigments which may be organic, inorganic or organometallic. In
another embodiment the invention encompasses multilayer articles
comprising a filled thermoset substrate layer such as a
sheet-molding compound (SMC).
The substrate layer may also comprise at least one cellulosic
material including, but not limited to, wood, paper, cardboard,
fiber board, particle board, plywood, construction paper, Kraft
paper, cellulose nitrate, cellulose acetate butyrate, and like
cellulosic-containing materials. The invention also encompasses
blends of at least one cellulosic material and either at least one
thermoset polymer (particularly an adhesive thermoset polymer), or
at least one thermoplastic polymer (particularly a recycled
thermoplastic polymer, such as PET or polycarbonate), or a mixture
of at least one thermoset polymer and at least one thermoplastic
polymer.
Multilayer articles encompassed by the invention also include those
comprising at least one glass layer. Typically any glass layer is a
substrate layer, although multilayer articles comprising a
thermally stable polymer coating layer interposed between a glass
layer and a substrate layer are also contemplated. Depending upon
the nature of coating and glass layers, at least one adhesive
interlayer may be beneficially employed between any glass layer and
any thermally stable polymer coating layer. The adhesive interlayer
may be transparent, opaque or translucent. For many applications it
is preferred that the interlayer be optically transparent in nature
and generally have a transmission of greater than about 60% and a
haze value less than about 3% with no objectionable color.
Metal articles exposed to UV-light may exhibit tarnishing and other
detrimental phenomena. Therefore, in another embodiment the
invention encompasses multilayer articles comprising at least one
metal layer as substrate layer. Representative metal substrates
include those comprising brass, copper, and other metals or
metal-containing articles which may require protection from
UV-light. Depending upon the nature of coating and metal layers, at
least one adhesive interlayer may be beneficially employed between
any metal layer and any thermally stable polymer coating layer.
Also present in the articles of the invention is at least one
coating layer comprising a thermoplastic polymer comprising
thermally stable resorcinol arylate polyester chain members
prepared by the method of the present invention. More particularly,
suitable coating layers comprise thermally stable resorcinol
arylate polyesters, copolyesters, (particularly those containing
soft-blocks), copolyestercarbonates, and mixtures thereof.
Copolyestercarbonates, when used in both substrate layer and in
coating layer, are different from each other in molecular
structure. More specifically, when the coating layer contains
copolyestercarbonate with resorcinol arylate polyester blocks, then
any ester blocks in the substrate copolyestercarbonate layer will
typically be derived from the same divalent organic radical as
contained in the carbonate blocks.
It is also within the scope of the invention for other polymers to
be present which are miscible in at least some proportions with the
polymer coating layer comprising thermally stable resorcinol
arylate polyester chain members. Illustrative examples of at least
partially miscible polymers include polyetherimide and polyesters
such as PBT, PET, PTT, PEN, PBN, PETG, PCCD, and bisphenol A
polyarylate. Preferably, the coating layer polymer consists
essentially of thermally stable resorcinol arylate polyesters,
copolyesters, or copolyestercarbonates.
Another aspect of the invention is a method for preparing a
multilayer article which comprises applying at least one thermally
stable coating layer to a second layer, said second layer
comprising at least one thermoplastic polymer, thermoset polymer,
cellulosic material, glass, or metal, and said coating layer
comprising a polymer comprising resorcinol arylate polyester chain
members substantially free of anhydride linkages linking at least
two mers of the polymer chain.
In the method of the invention, at least one thermally stable
coating layer is applied to a second layer, which may be the
substrate layer or at least one intermediate layer ultimately to be
disposed between the coating and substrate layers. An intermediate
layer may generally comprise any of the materials suitable for use
as the substrate or coating layer, and may further contain fillers
and colorants such as described hereinabove. When necessary, it may
be specifically chosen so as to provide good adhesion between
substrate and coating layers. Colorants of the previously described
types may also be present in the coating layer.
Application of the at least one coating layer may be performed by
solvent-casting. More preferably, application of said coating layer
comprises fabrication of a separate sheet thereof followed by
application to the second layer, or by simultaneous production of
both layers, typically in a melt process. Thus, there may be
employed such methods as co-injection molding, coextrusion,
overmolding, blow molding, multi-shot injection molding and
placement of a film of the coating layer material on the surface of
the second layer followed by adhesion of the two layers, typically
in an injection molding apparatus; e.g., in-mold decoration, or in
a hot-press. These operations may be conducted under art-recognized
conditions.
It is also within the scope of the invention to apply a structure
comprising the coating layer and the second layer to a third,
substrate layer, which is generally of a thermoplastic, thermoset,
or cellulosic material similar or identical to that of the second
layer but different from that of the coating layer. This may be
achieved, for example, by charging an injection mold with the
structure comprising the coating layer and the second layer and
injecting the substrate sheet material behind it. By this method,
in-mold decoration and the like are possible. Both sides of the
substrate layer may receive the other layers, though it is usually
preferred to apply them to only one side.
The thicknesses of the v arious layers in multilayer articles of
this invention are most often as follows: substrate--at least 125
.mu.(microns), preferably at least about 250.mu., more preferably
at least about 400.mu., coating--about 2-2,500, preferably about
10-250 and most preferably about 50-175.mu., second material, if
any--about 2-2,500, preferably about 10-250, and most preferably
about 50-175.mu., total--at least about 125.mu., preferably at
least about 250.mu., more preferably at least about 400.mu..
The articles of this invention are characterized by the usual
beneficial properties of the substrate layer, in addition to
weatherability as evidenced by improved resistance to ultraviolet
radiation and maintenance of gloss, and solvent resistance.
Depending upon the coating layer/substrate combination, the
multilayer articles may possess recycling capability, which makes
it possible to employ the regrind material as a substrate for
further production of articles of the invention.
Multilayer articles which can be made which comprise thermally
stable polymers comprising resorcinol arylate polyester chain
members include automotive, truck, military vehicle, and motorcycle
exterior and interior components, including panels, quarter panels,
rocker panels, trim, fenders, doors, decklids, trunklids, hoods,
bonnets, roofs, bumpers, fascia, grilles, mirror housings, pillar
appliques, cladding, body side moldings, wheel covers, hubcaps,
door handles, spoilers, window frames, headlamp bezels, headlamps,
tail lamps, tail lamp housings, tail lamp bezels, license plate
enclosures, roof racks, and running boards; enclosures, housings,
panels, and parts for outdoor vehicles and devices; enclosures for
electrical and telecommunication devices; outdoor furniture;
aircraft components; boats and marine equipment, including trim,
enclosures, and housings; outboard motor housings; depth finder
housings, personal water-craft; jet-skis; pools; spas; hot-tubs;
steps; step coverings; building and construction applications such
as glazing, roofs, windows, floors, decorative window furnishings
or treatments; treated glass covers for pictures, paintings,
posters, and like display items; wall panels, and doors; protected
graphics; outdoor and indoor signs; enclosures, housings, panels,
and parts for automatic teller machines (ATM); enclosures,
housings, panels, and parts for lawn and garden tractors, lawn
mowers, and tools, including lawn and garden tools; window and door
trim; sports equipment and toys; enclosures, housings, panels, and
parts for snowmobiles; recreational vehicle panels and components;
playground equipment; articles made from plastic-wood combinations;
golf course markers; utility pit covers; computer housings;
desk-top computer housings; portable computer housings; lap-top
computer housings; palm-held computer housings; monitor housings;
printer housings; keyboards; FAX machine housings; copier housings;
telephone housings; mobile phone housings; radio sender housings;
radio receiver housings; light fixtures; lighting appliances;
network interface device housings; transformer housings; air
conditioner housings; cladding or seating for public
transportation; cladding or seating for trains, subways, or buses;
meter housings; antenna housings; cladding for satellite dishes;
coated helmets and personal protective equipment; coated synthetic
or natural textiles; coated photographic film and photographic
prints; coated painted articles; coated dyed articles; coated
fluorescent articles; coated foam articles; and like applications.
The invention further contemplates additional fabrication
operations on said articles, such as, but not limited to, molding,
in-mold decoration, baking in a paint oven, lamination, and/or
thermoforming.
This invention has been described in detail with particular
reference to preferred embodiments thereof, but it will be
understood that variations and modifications can be effected within
the spirit and scope of the invention.
The invention is illustrated by the following, non-limiting
examples. All parts are by weight unless otherwise designated.
Molecular weight values for polymeric samples were determined by
gel permeation chromatography (GPC) using 3% isopropanol/chloroform
eluent at 0.75 milliliters (ml) per minute (min) on a Polymer Labs
Mixed C size exclusion column held at 35.degree. C., and calibrated
using polystyrene standards, and analyzed with Turbogel
software.
EXAMPLE 1
This example illustrates the preparation of a thermally stable
resorcinol arylate polyester with both iso- and terephthalate
units. To a one liter, five neck, Morton flask blanketed with
nitrogen and equipped with a mechanical stirrer, pH electrode,
reflux condenser, two pressure equalizing addition funnels, was
charged resorcinol (21.8 grams [g]; 0.198 moles [mol]), resorcinol
monobenzoate capping agent (1.07 g; 2.5 mole %), triethylamine
(0.274 ml; 1 mole %), dichloromethane (150 ml), and water (100 ml).
One addition funnel was charged with sodium hydroxide pellets
(16.84 g; 0.42 mol) and water (32 ml), while a solution of
isophthaloyl dichloride (20.3 g; 0.1 mol), terephthaloyl dichloride
(20.3 g; 0.1 mol), and dichloromethane (150 ml) was added to the
second. The pH of the reaction mixture was adjusted to 7.5 with
sodium hydroxide prior to the addition of acid chloride solutions,
which were added over 6 minutes. The pH of the reaction was
maintained between 7.25 and 7.75 for the first ten minutes of
reaction. At 11 minutes the reaction pH was raised to about 10 with
the addition of sodium hydroxide and held for an additional 10
minutes. The stirring was stopped and the aqueous layer was
removed. The resulting gray organic layer was washed with 1N
hydrochloric acid, 0.1N hydrochloric acid, water (three times), and
the polymer isolated by precipitation into boiling water yielding a
white, fibrous material which was dried in vacuum at 110.degree. C.
overnight. The isolated polymer was the desired resorcinol arylate
polyester.
Control Example 1
A polyester of resorcinol with a mixture of iso- and terephthalate
was prepared in a blender according to the interfacial method of
U.S. Pat. No. 3,460,961. The isolated polymer had weight average
molecular weight of about 289,000. The procedure was modified by
addition of 4 mole % chain-stopper (phenol), resulting in polymer
with weight average molecular weight of about 51,000.
Control Example 2
A polyester of resorcinol with a mixture of iso- and terephthalate
was prepared according to the solution method of Cohen et al.,
Journal of Polymer Science: Part A-1, vol. 9, 3263-3299 (1971). To
a one-liter, three neck, round bottomed flask equipped with a
mechanical stirrer and an addition funnel were charged isophthaloyl
chloride (5.076 g, 25 millimoles [mmol]), terephthaloyl chloride
(5.076 g, 25 mmol), resorcinol (5.506 g, 50 mmol), and
tetrahydrofuran (200 ml) dried by distillation from sodium and
benzophenone. Polymerization was initiated by dropwise addition of
a stoichiometric amount of triethylamine (10.12 g, 10 mmol) over 30
minutes. The mixture then was stirred for 3 hours at room
temperature. Triethylamine hydrochloride was removed from the
reaction mixture by filtration. The filtrate was slowly poured into
methanol (500 ml) in a blender. The precipitated polymer was washed
with hot water and dried in a vacuum oven. The isolated polymer had
weight average molecular weight of about 47,000.
EXAMPLES 2-11
These examples illustrate the preparation of hydroxy-terminated
resorcinol iso/terephthalate oligomers. Into a 1 liter Morton flask
equipped with a mechanical stirrer, pH electrode, condenser, and
two addition tubes connected to metering pumps were charged
resorcinol (12.11 g, 0.11 mol), water (18 ml), methylene chloride
(200 ml), and triethylamine (140 to 560 microliters, 1 to 4 mol %
based on acid chlorides). The mixture was stirred at 500 rpm. A
two-step addition profile was used for the delivery of acid
chloride solution and base solution. In the first step, a majority
of base (60 to 80% out of total base amount of 17.5 ml of 33%
aqueous sodium hydroxide solution) and the whole acid chloride
solution (70 ml solution of isophthaloyl chloride (10.15 g, 0.05
mol) and terephthaloyl chloride (10.15 g, 0.05 mol) in methylene
chloride) were added at constant rates, and the remaining base was
added in the second step at continuously decreasing rate. The base
was pumped from graduated burets and the amount was checked every
30 seconds in order to control the stoichiometry. The pH varied
between about 3.5 and about 8. The length of the first step was
varied from 7 to 13 minutes with the total step 1 and step 2 time
constant at 25 minutes. The reaction mixture was further stirred
for 30 minute total reaction time. The reaction conditions and
weight average molecular weights of the isolated polymers are shown
in Table 1.
TABLE-US-00001 TABLE 1 % Base Added Base Addition mol % Oligomer
Example in 1st Step time (min.) triethylamine Mw.sup.a 2 60 7 1
27.3 3 60 7 4 26.9 4 60 13 4 24.5 5 60 13 1 26 6 70 10 2.5 28.3 7
70 10 2.5 23 8 80 7 4 28.4 9 80 7 1 30.8 10 80 13 4 29.5 11 80 13 1
38.4 .sup.atimes 10.sup.-3
A sample of each polymer was analyzed for anhydride content by
treatment in solution with diisobutylamine. Polymers prepared using
4 mol % triethylamine showed greater than 95% retention of weight
average molecular weight.
EXAMPLES 12-28
The procedure of Examples 2-11 was repeated except that in some
experiments 13 to 15 mol % total excess of resorcinol was used. In
some experiments a small amount of capping agent (1 mol % phenol)
was added. In some cases, the reaction mixture was heated
externally to a refluxing point at 3 minutes. The reaction
conditions and weight average molecular weights of the isolated
polymers are shown in Table 2.
TABLE-US-00002 TABLE 2 mol % Initial % Mw Example triethylamine
Comments.sup.a Reflux.sup.b Mw.sup.c Retention.sup.d- 12 4 1% PhOH
Y 19.5 99 13 4 15% excess Rs N 19.5 100 14 4 0.5% PhOH N 21.6 99.5
15 4 15% excess Rs Y 21.8 96.6 16 4 1% PhOH N 21.9 99.3 17 4 1%
PhOH Y 22.3 97.7 18 4 N 22.3 96.1 19 4 13% excess Rs N 22.4 97.7 20
4 1% PhOH Y 22.4 96.4 21 4 1% PhOH Y 22.5 93 22 4 1% PhOH N 22.7
97.8 23 4 0.5 PhCOCl N 24.6 99 24 2.5 1% PhOH Y 24.7 97.2 25 4 N
24.8 96.7 26 4 Y 25.3 98 27 4 N 26.6 97.7 28 3 Y 30.3 100
.sup.aPhOH (phenol); Rs (resorcinol); PhCOCl (benzoyl chloride)
.sup.bY (Yes); N (No) .sup.ctimes 10.sup.-3 .sup.dfollowing
treatment with diisobutylamine in solution
EXAMPLES 29-46
The procedure of Examples 2-11 was repeated except that a portion
of tertiary amine was added following addition of dicarboxylic acid
dichloride to resorcinol moiety. A total of 4 mol % tertiary amine
(40000 ppm; based on moles acid chlorides) was added. The reaction
conditions and weight average molecular weights of the isolated
polymers are shown in Table 3. Example 46 is a control experiment
in which all the tertiary amine was present at the beginning of the
reaction before addition of dicarboxylic acid dichloride to
resorcinol moiety
TABLE-US-00003 TABLE 3 Base TEA Ex- % Base Addition added am Added
in time initially % Mw ple 1st Step (min.) (ppm) Initial Mw.sup.a
Retention.sup.b 29 80 7 50 29.3 96.5 30 80 7 10 23.1 86.8 31 80 7
10 22.2 98.5 32 80 7 50 29.4 97.4 33 96 7 10 32.7 94.3 34 96 7 50
34.4 92.5 35 88 10 30 26.5 99.4 36 88 10 30 25.6 101 37 80 13 50
25.9 95.9 38 80 13 10 25.2 96.6 39 96 13 50 29.4 90.2 40 96 13 10
22.14 98.59 41 96 13 50 26.7 92.93 42 96 13 10 23.6 90.5 43 96 16
10 21.6, 22.0 98.8, 98.0 44 96 19 10 24.1, 22.3 95.9, 97.3 45 64 7
10 21.46, 23.32 96.3, 100 46 96 16 40000 24.7, 23.1 92.7, 94.4
.sup.atimes 10.sup.-3 .sup.bfollowing treatment with
diisobutylamine in solution
EXAMPLE 47
This example illustrates the preparation of a thermally stable
resorcinol iso/terephthalate-block-copolycarbonate beginning with
the preparation of hydroxy-terminated resorcinol iso/terephthalate
oligomer. To a thirty liter glass reactor equipped with a glass
impeller, centrifuge recirculation pump, reflux condenser and
pressure equilibration addition funnel were charged resorcinol
(605.6 g, 5.5 mol), methyltributylammonium chloride (82.5 g of a
75% wt. aqueous solution; 0.275 mol), dichloromethane (6.5 liters),
and water (2.5 liters). The recirculation pump was turned on and
the mixture was degassed with nitrogen while stirring. The pH of
the aqueous phase was adjusted to 7 with 50% aqueous sodium
hydroxide solution. Reaction was carried out by adding a solution
of acid chlorides (507.5 g each of iso- and terephthaloyl
dichlorides; 5.00 moles total in 2.0 liters of dichloromethane
solution) while stirring and simultaneously adding 50% sodium
hydroxide solution at such a rate that the pH was maintained
between 6 and 8. The acid chlorides were added using a three-step
program with the rate of addition declining with each step. A timer
was started at the beginning of acid chloride addition. The pH was
maintained at 8 while adding acid chlorides over 8 minutes using
the following protocol: 40% of total acid chlorides was added over
the first 2 minutes; 30% of total was added over the next 2
minutes; the remaining 30% of total was added over the next 4
minutes. The recirculation loop was running during the entire
time.
Following complete addition of acid chlorides, the pH was slowly
raised to 11-12 over two to three minutes, and the reaction mixture
was stirred for 10 minutes. The polymer formed was a
hydroxy-terminated oligomer with weight average molecular weight
(Mw) of approximately 20,000.
Bisphenol A (1102 g, 4.83 mol), dichloromethane (4.0 liters),
triethylamine (17 ml, 0.12 mol), p-cumyl phenol capping agent (60
g), and water (6.0 liters) were then added and the recirculation
loop was turned on. Phosgene was introduced at pH 7.5-8.5, then
increasing slowly to pH 10-10.5 using a 15% excess over the
theoretical amount of phosgene.
The reaction mixture was separated, the organic phase washed with
1N hydrochloric acid, 0.1N hydrochloric acid, and twice with water,
and the polymer was isolated by precipitation in methanol. The
polymer obtained was the desired resorcinol
iso/terephthalate-co-BPA polycarbonate copolymer.
EXAMPLES 48-61
Samples of polymers comprising resorcinol arylate polyester chain
members were dried in vacuo at 120.degree. C. for 15 hrs. A
weighted sample of about 25-30 milligrams was placed in a circular
die cavity 2 centimeters (cm.) in diameter and covered with a
cylindrical piston of the same size. The die assembly containing
the sample was heated in a Carver press at 290.degree. C. for 5
minutes at 500-4,000 pounds gauge (lbs.g.) pressure, then removed
and cooled in chill blocks. The heat treatment produced a film
about 1 mil in thickness and 2 cm. in diameter. Molecular weights
of samples before and after the heat treatment were measured by GPC
using polystyrene standards. Table 4 shows examples of melt
stability for resorcinol arylate polyesters prepared using the
method of Example 1 and Control Examples 1 and 2, and for
resorcinol arylate-containing copolyestercarbonates prepared using
the method of Example 47. Wt. % resorcinol arylate in the Table
refers to wt. % resorcinol arylate chain members in the polymer,
the remaining mers being organic carbonate mers.
TABLE-US-00004 TABLE 4 wt. % % Mw resorcinol % Mw Retention,
Retention, Example arylate mell processing.sup.f amine test.sup.g
48.sup.a 50 89.4 98 49.sup.a 80 84 97.9 50.sup.a 50 84.8 94
51.sup.b 50 98.8 99.5 52.sup.b 35 98.7 99.3 53.sup.c 100 55 62
54.sup.c 100 55.9 61 55.sup.b 100 45 40 56.sup.b 100 87.5 86
57.sup.b 100 97.7 99.6 58.sup.b 100 99.5 99 59.sup.a 100 12 25
60.sup.d 100 46 74 61.sup.e 100 77 78 .sup.afinal reaction mixture
stirred 5 min at pH 10 .sup.bfinal reaction mixture stirred 30 min
at pH 10-12 .sup.cControl Example 1 .sup.dControl Example 1 using 4
mole % phenol chain-stopper .sup.eControl Example 2 .sup.ffollowing
extrusion .sup.gfollowing treatment with diisobutylamine in
solution
EXAMPLE 62
A resorcinol arylate polyester was prepared by the interfacial
method of Control Example 1 except that the organic solvent was
dichloromethane and a capping agent was present. Extrusion of the
material gave orange pellets. The polymer had initial weight
average molecular weight (Mw) of 61,300 and Mw after extrusion of
52,200 (85% retention). A separate sample of material was treated
with dibutylamine in solution; the Mw of the recovered material was
42,400 (69% retention).
EXAMPLE 63
A resorcinol arylate polyester was prepared by the method of
Example 1. Extrusion of the material gave yellowish pellets. The
polymer had initial Mw of 53,600 and Mw after extrusion of 50,800
(95% retention). A separate sample of material was treated with
dibutylamine in solution; the Mw of the recovered material was
48,400 (90% retention).
EXAMPLE 64
A resorcinol arylate-containing block copolyestercarbonate with 50%
by weight carbonate blocks and 1:1 ratio of isophthalate to
terephthalate in the resorcinol arylate blocks was prepared by the
method of Example 47 except that the resorcinol arylate-containing
polyester block was made using the procedure of Control Example 1
using a capping agent and dichloromethane as the organic solvent.
Extrusion of the material gave amber pellets. The copolymer had
initial Mw of 75,900 and Mw after extrusion of 64,500 (85%
retention). A separate sample of material was treated with
dibutylamine in solution; the Mw of the recovered material was
73,000 (96% retention).
EXAMPLE 65
A resorcinol arylate-containing block copolyestercarbonate was
prepared by the method of Example 47 with 50% by weight carbonate
blocks and 1:1 ratio of isophthalate to terephthalate in the
resorcinol arylate blocks. Extrusion of the material gave faintly
yellowish pellets. The copolymer had initial Mw of 52,300 and Mw
after extrusion of 51,700 (99% retention). A separate sample of
material was treated with dibutylamine in solution; the Mw of the
recovered material was 51,500 (98% retention).
Disks were formed from the resorcinol arylate-containing polymers
of Examples 62-65. The disks were approximately 0.6 millimeters
(mm) (0.024 inches) thick and 50 mm (2.0 inches) diameter, and were
formed from melt-processed polymer (either pellets, extruded film,
or injection molded parts) under the following conditions: 2.1 g of
melt-processed polymer were placed in a mold between heated platens
of a hydraulic press and heated at about 200.degree. C. with no
applied pressure for 3 minutes, then under 4500 lbs.g. pressure for
1 minute, and finally under 6500 lbs.g. pressure for 1 minute. The
mold was then rapidly cooled in ice water and opened to remove the
disk.
The disks prepared as described were laminated onto
injection-molded plaques of LEXAN 140 polycarbonate (from General
Electric Plastics) containing 2 wt. % of TiO.sub.2 pigment under
the following conditions to make well-adhered multilayer articles.
All materials were placed in a heated (60.degree. C.) vacuum
desiccator overnight. A disk was placed onto an injection molded
plaque of polycarbonate 2.5 inches square and one-eighth inch thick
in a mold between heated platens of a hydraulic press and heated at
about 200.degree. C. with no applied pressure for 2 minutes, then
under 4500 lbs.g. pressure for 1 minute, and finally under 6500
lbs.g. pressure for 1 minute. All samples were well adhered.
The color of the disks and of the laminated plaques was determined
on a Macbeth 7000 Color-Eye colorimeter and reported as CIELAB
values and yellowness index (YI; according to ASTM D1925). Results
are shown on Table 5.
TABLE-US-00005 TABLE 5 Disks (transmission) Laminate on PC
(reflection) Example L.sup.+ a.sup.+ b.sup.+ YI L.sup.+ a.sup.+
b.sup.+ YI 62 90.45 -1.23 15.2 26.01 76.6 3.57 31.74 61.07 63 94.73
-0.3 3.61 6.34 86.18 -0.38 14.95 27.4 64 93.82 -0.43 5.4 9.5 84.21
0.88 20.44 38.27 65 95.52 -0.11 1.31 2.26 91.21 -0.8 6.95 12
unlaminated 94.86 -0.52 2.88 4.51 PC
The data show that the disks and multilayer articles formed from
melt-processed resorcinol arylate-containing polymers made by the
method of the invention have much less color and lower yellowness
index than the respective control blends.
* * * * *