U.S. patent application number 11/813833 was filed with the patent office on 2008-06-12 for flowable polyester with protection against hydrolysis.
This patent application is currently assigned to BASF Aktiengesellschaft. Invention is credited to Bernd Bruchmann, Andreas Eipper, Michaela Liese, Dietrich Scherzer, Jean-Francois Stumbe, Mark Volkel, Carsten Weiss.
Application Number | 20080139712 11/813833 |
Document ID | / |
Family ID | 36337561 |
Filed Date | 2008-06-12 |
United States Patent
Application |
20080139712 |
Kind Code |
A1 |
Scherzer; Dietrich ; et
al. |
June 12, 2008 |
Flowable Polyester With Protection Against Hydrolysis
Abstract
Thermoplastic molding compositions, comprising A) from 10 to
98.9% by weight of at least one thermoplastic polyester, B) from
0.01 to 50% by weight of B1) at least one highly branched or
hyperbranched polycarbonate or B2) at least one highly branched or
hyperbranched polyester of A.sub.xB.sub.y type, where x is at least
1.1 and y is at least 2.1 or a mixture of these C) from 0.1 to 10%
by weight of at least one epoxidized naturally occurring oil or
fatty acid ester, or a mixture of these, and D) from 0 to 60% by
weight of other additives, where the total of the percentages by
weight of components A) to D) is 100%.
Inventors: |
Scherzer; Dietrich;
(Neustadt, DE) ; Bruchmann; Bernd; (Freinsheim,
DE) ; Eipper; Andreas; (Ludwigshafen, DE) ;
Stumbe; Jean-Francois; (Strasbourg, DE) ; Weiss;
Carsten; (Singapore, SG) ; Liese; Michaela;
(Ludwigshafen, DE) ; Volkel; Mark; (Ladenburg,
DE) |
Correspondence
Address: |
CONNOLLY BOVE LODGE & HUTZ, LLP
P O BOX 2207
WILMINGTON
DE
19899
US
|
Assignee: |
BASF Aktiengesellschaft
Ludwigshafen
DE
|
Family ID: |
36337561 |
Appl. No.: |
11/813833 |
Filed: |
December 31, 2005 |
PCT Filed: |
December 31, 2005 |
PCT NO: |
PCT/EP05/14165 |
371 Date: |
July 12, 2007 |
Current U.S.
Class: |
524/114 |
Current CPC
Class: |
C08L 67/00 20130101;
C08L 67/02 20130101; C08L 91/00 20130101; C08L 69/00 20130101; C08L
67/02 20130101; C08L 101/005 20130101; C08G 64/0216 20130101; C08L
2666/02 20130101; C08L 63/00 20130101; C08L 67/00 20130101; C08L
69/00 20130101; C08L 2666/18 20130101; C08L 67/02 20130101; C08L
67/02 20130101; C08L 67/02 20130101 |
Class at
Publication: |
524/114 |
International
Class: |
C08K 5/1515 20060101
C08K005/1515 |
Foreign Application Data
Date |
Code |
Application Number |
Jan 14, 2005 |
DE |
10 2005 002 044.5 |
Claims
1-13. (canceled)
14. A thermoplastic molding composition, comprising A) from 10 to
98.9% by weight of at least one thermoplastic polyester; B) from
0.01 to 50% by weight of B 1) at least one highly branched or
hyperbranched polycarbonate; or B2) at least one highly branched or
hyperbranched polyester of A.sub.xB.sub.y type, wherein x is at
least 1.1 and y is at least 2.1; or B3) mixtures of B1) and B2); C)
from 0.1 to 10% by weight of C1) at least one epoxidized naturally
occurring oil; C2) at least one epoxidized naturally occurring
fatty acid ester; or C3) mixtures of C1) and C2); and D) from 0 to
60% by weight of other additives; wherein the total of the
percentages by weight of components A), B), C), and D) is equal to
100%.
15. The thermoplastic molding composition of claim 14, wherein B1)
has a number-average molar mass of from 100 to 15 000 g/mol.
16. The thermoplastic molding composition of claim 14, wherein B1)
has a glass transition temperature of from -80 .degree. C. to 140
.degree. C.
17. The thermoplastic molding composition of claim 14, wherein B1)
has a viscosity at 23 .degree. C. of from 50 to 200 000 mPas.
18. The thermoplastic molding composition of claim 14, wherein B 1)
has an OH number of from 1 to 600 mg KOH/g of polycarbonate.
19. The thermoplastic molding composition of claim 14, wherein B2)
has a number-average molar mass of from 300 to 30 000 g/mol.
20. The thermoplastic molding composition of claim 14, wherein B2)
has a glass transition temperature of from -50 .degree. C. to 140
.degree. C.
21. The thermoplastic molding composition of claim 14, wherein B2)
has an OH number of from 0 to 600 mg KOH/g of polyester.
22. The thermoplastic molding composition of claim 14, wherein B2)
has a COOH number of from 0 to 600 mg KOH/g of polyester.
23. The thermoplastic molding composition of claim 14, wherein B2)
has at least one OH number or COOH number greater than 0.
24. The thermoplastic molding composition of claim 14, wherein the
ratio of B1) to B2) is from 1:20 to 20:1.
25. A fiber, foil, or molding of any type comprising the
thermoplastic molding composition of claim 14.
Description
[0001] The invention relates to thermplastic molding compositions,
comprising [0002] A) from 10 to 98.9% by weight of at least one
thermoplastic polyester, [0003] B) from 0.01 to 50% by weight of
[0004] B1) at least one highly branched or hyperbranched
polycarbonate or [0005] B2) at least one highly branched or
hyperbranched polyester of A.sub.xB.sub.y type, where x is at least
1.1 and y is at least 2.1 or a mixture of these [0006] C) from 0.1
to 10% by weight of at least one epoxidized naturally occurring oil
or fatty acid ester, or a mixture of these, and [0007] D) from 0 to
60% by weight of other additives, where the total of the
percentages by weight of components A) to D) is 100%.
[0008] The invention further relates to the use of the inventive
molding compositions for production of fibers, of foils, and of
moldings, and also to the resultant moldings of any type.
[0009] Low-molecular-weight additives are usually added to
thermoplastics in order to improve flowability. However, the action
of these additives is subject to severe restriction, because, for
example, the fall-off in mechanical properties becomes unacceptable
when the added amount of the additive increases
[0010] Dendritic polymers having a perfectly symmetrical structure,
known as dendrimers, can be prepared starting from one central
molecule via controlled stepwise linkage of, in each case, two or
more di- or polyfunctional monomers to each previously bonded
monomer. Each linkage step here exponentially increases the number
of monomer end groups (and therefore of linkages), and this gives
polymers with dendritic structures, in the ideal case spherical,
the branches of which comprise exactly the same number of monomer
units. This perfect structure provides advantageous polymer
properties, and by way of example surprisingly low viscosity is
found, as is high reactivity, due to the large number of functional
groups on the surface of the sphere. However, the preparation
process is complicated by the fact that protective groups have to
be introduced and in turn removed again during each linkage step,
and purification operations are required, the result being that it
is usual for dendrimers to be prepared only on a laboratory scale.
However, highly branched or hyperbranched polymers can be prepared
using industrial processes. They also have linear polymer chains
and unequal polymer branches alongside perfect dendritic
structures, but this does not substantially impair the properties
of the polymer when comparison is made with perfect dendrimers.
Hyperbranched polymers can be prepared via two synthetic routes
known as AB.sub.2 and A.sub.x+B.sub.y. A.sub.x and B.sub.y here are
different monomers and the indices x and y are the number of
functional groups present in A and B respectively, i.e. the
functionality of A and B, respectively. In the AB.sub.2 route, a
trifunctional monomer having a reactive group A and having two
reactive groups B is reacted to give a highly branched or
hyperbranched polymer. In the A.sub.xand B.sub.y synthesis, taking
the example of A.sub.2+B3 synthesis, a difunctional monomer A.sub.2
is reacted with a trifunctional monomer B.sub.3. This first gives a
1:1 adduct composed of A and B having an average of one functional
group A and two functional groups B, and this can then likewise
react to give a highly branched or hyperbranched polymer.
[0011] WO-97/45474 discloses thermoplastic compositions which
comprise dendrimeric polyesters as AB.sub.2 molecule. Here, a
polyhydric alcohol as core molecule reacts with dimethylolpropionic
acid as AB.sub.2 molecule to give a dendrimeric polyester. This
comprises only OH functions at the end of the chain. Disadvantages
of these mixtures are high glass transition temperature of the
dendrimeric polyesters, comparatively complicated preparation
process, and especially poor solubility of the dendrimers in the
polyester matrix.
[0012] According to the teaching of DE-A 101 32 928, the
incorporation of branching agents of this type by means of
compounding and solid-phase post-condensation leads to an
improvement in mechanical properties (molecular weight increase).
The disadvantages of the process variant described are long
preparation time and the disadvantageous properties listed
above.
[0013] DE 102004 005652.8 and DE 102004 005657.9 have previously
proposed novel additives for flow improvement in polyesters.
[0014] An object underlying the present invention was therefore to
provide thermoplastic polyester molding compositions which have
good flowability together with good mechanical properties. In
particular, the additives (or the additive combination) is intended
neither to exude nor to have any tendency to form mold deposit.
[0015] The inventive molding compositions comprise, as component
(A), from 10 to 98.9% by weight, preferably from 30 to 97% by
weight, and in particular from 30 to 95% by weight, of at least one
thermoplastic polyester.
[0016] Use is generally made of polyesters A) based on aromatic
dicarboxylic acids and on an aliphatic or aromatic dihydroxy
compound.
[0017] A first group of preferred polyesters is that of
polyalkylene terephthalates, in particular those having from 2 to
10 carbon atoms in the alcohol moiety.
[0018] Polyalkylene terephthalates of this type are known per se
and are described in the literature. Their main chain comprises an
aromatic ring which derives from the aromatic dicarboxylic acid.
There may also be substitution in the aromatic ring, e.g. by
halogen, such as chlorine or bromine, or by C.sub.1-C.sub.4-alkyl,
such as methyl, ethyl, iso- or n-propyl, or n-, iso- or
tert-butyl.
[0019] These polyalkylene terephthalates may be prepared by
reacting aromatic dicarboxylic acids, or their esters or other
esterforming derivatives, with aliphatic dihydroxy compounds in a
manner known per se.
[0020] Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic
acid, terephthalic acid and isophthalic acid, and mixtures of
these. Up to 30 mol %, preferably not more than 10 mol % of the
aromatic dicarboxylic acids may be replaced by aliphatic or
cycloaliphatic dicarboxylic acids, such as adipic acid, azelaic
acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic
acids.
[0021] Preferred aliphatic dihydroxy compounds are diols having
from 2 to 6 carbon atoms, in particular 1,2-ethanediol,
1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-hexanediol,
1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and neopentyl
glycol, and mixtures of these.
[0022] Particularly preferred polyesters (A) are polyalkylene
terephthalates derived from alkanediols having from 2 to 6 carbon
atoms. Among these, particular preference is given to polyethylene
terephthalate, polypropylene terephthalate and polybutylene
terephthalate, and mixtures of these. Preference is also given to
PET and/or PBT which comprise, as other monomer units, up to 1% by
weight, preferably up to 0.75% by weight, of 1,6-hexanediol and/or
2-methyl-1,5-pentanediol.
[0023] The viscosity number of the polyesters (A) is generally in
the range from 50 to 220, preferably from 80 to 160 (measured in
0.5% strength by weight solution in a phenol/o-dichlorobenzene
mixture in a weight ratio of 1:1 at 25.degree. C.) in accordance
with ISO 1628.
[0024] Particular preference is given to polyesters whose carboxyl
end group content is up to 100 meq/kg of polyester, preferably up
to 50 meq/kg of polyester and in particular up to 40 meq/kg of
polyester. Polyesters of this type may be prepared, for example, by
the process of DE-A 44 01 055. The carboxyl end group content is
usually determined by titration methods (e.g. potentiometry).
[0025] Particularly preferred molding compositions comprise, as
component A), a mixture of polyesters other than PBT, for example
polyethylene terephthalate (PET). The proportion of the
polyethylene terephthalate, for example, in the mixture is
preferably up to 50% by weight, in particular from 10 to 35% by
weight, based on 100% by weight of A).
[0026] It is also advantageous to use recycled PET materials (also
termed scrap PET), if appropriate mixed with polyalkylene
terephthalates, such as PBT.
[0027] Recycled materials are generally: [0028] 1) those known as
post-industrial recycled materials: these are production wastes
during polycondensation or during processing, e.g. sprues from
injection molding, start-up material from injection molding or
extrusion, or edge trims from extruded sheets or foils. [0029] 2)
post-consumer recycled materials: these are plastic items which are
collected and treated after utilization by the end consumer.
Blow-molded PET bottles for mineral water, soft drinks and juices
are easily the predominant items in terms of quantity.
[0030] Both types of recycled material may be used either as ground
material or in the form of pellets. In the latter case, the crude
recycled materials are separated and purified and then melted and
pelletized using an extruder. This usually facilitates handling and
free flow, and metering for further steps in processing.
[0031] The recycled materials used may be either pelletized or in
the form of regrind. The edge length should not be more than 10 mm,
preferably less than 8 mm.
[0032] Because polyesters undergo hydrolytic cleavage during
processing (due to traces of moisture) it is advisable to predry
the recycled material. The residual moisture content after drying
is preferably <0.2%, in particular <0.05%.
[0033] Another group to be mentioned is that of fully aromatic
polyesters derived from aromatic dicarboxylic acids and aromatic
dihydroxy compounds.
[0034] Suitable aromatic dicarboxylic acids are the compounds
previously mentioned for the polyalkylene terephthalates. The
mixtures preferably used are composed of from 5 to 100 mol % of
isophthalic acid and from 0 to 95 mol % of terephthalic acid, in
particular mixtures of about 80% of terephthalic acid and about 20%
of isophthalic acid, up to approximately equivalent mixtures of
these two acids.
[0035] The aromatic dihydroxy compounds preferably have the general
formula
##STR00001##
where Z is an alkylene or cycloalkylene group having up to 8 carbon
atoms, an arylene group having up to 12 carbon atoms, a carbonyl
group, a sulfonyl group, an oxygen or sulfur atom, or a chemical
bond, and m is from 0 to 2. The phenylene groups of the compounds
may also have substitution by C.sub.1-C.sub.6-alkyl or alkoxy and
fluorine, chlorine or bromine.
[0036] Examples of parent compounds for these compounds are [0037]
dihydroxybiphenyl, [0038] di(hydroxyphenyl)alkane, [0039]
di(hydroxyphenyl)cycloalkane, [0040] di(hydroxyphenyl) sulfide,
[0041] di(hydroxyphenyl) ether, [0042] di(hydroxyphenyl) ketone,
[0043] di(hydroxyphenyl) sulfoxide, [0044]
.alpha.,.alpha.'-di(hydroxyphenyl)dialkylbenzene, [0045]
di(hydroxyphenyl) sulfone, di(hydroxybenzoyl)benzene, [0046]
resorcinol, and [0047] hydroquinone, and also the ring-alkylated
and ring-halogenated derivatives of these.
[0048] Among these, preference is given to [0049]
4,4'-dihydroxybiphenyl, [0050]
2,4-di(4'-hydroxyphenyl)-2-methylbutane, [0051]
.alpha.,.alpha.'-di(4-hydroxyphenyl)-p-diisopropylbenzene, [0052]
2,2-di(3'-methyl-4'-hydroxyphenyl)propane, and [0053]
2,2-di(3'-chloro-4'-hydroxyphenyl)propane, and in particular to
[0054] 2,2-di(4'-hydroxyphenyl)propane [0055]
2,2-di(3',5-dichlorodihydroxyphenyl)propane, [0056] 1,
1-di(4'-hydroxyphenyl)cyclohexane, [0057]
3,4'-dihydroxybenzophenone, [0058] 4,4'-dihydroxydiphenyl sulfone
and [0059] 2,2-di(3',5'-dimethyl-4'-hydroxyphenyl)propane and
mixtures of these.
[0060] It is, of course, also possible to use mixtures of
polyalkylene terephthalates and fully aromatic polyesters. These
generally comprise from 20 to 98% by weight of the polyalkylene
terephthalate and from 2 to 80% by weight of the fully aromatic
polyester.
[0061] It is, of course, also possible to use polyester block
copolymers, such as copolyetheresters. Products of this type are
known per se and are described in the literature, e.g. in U.S. Pat.
No. 3,651,014. Corresponding products are also available
commercially, e.g. Hytrel.RTM. (DuPont).
[0062] According to the invention, polyesters include halogen-free
polycarbonates. Examples of suitable halogen-free polycarbonates
are those based on diphenols of the general formula
##STR00002##
where Q is a single bond, a C.sub.1-C.sub.8-alkylene,
C.sub.2-C.sub.3- alkylidene, C.sub.3-C.sub.6-cycloalkylidene,
C.sub.6-C.sub.12-arylene group, or --O--, --S-- or --SO.sub.2--,
and m is a whole number from 0 to 2.
[0063] The phenylene radicals of the diphenols may also have
substituents, such as C.sub.1-C.sub.6-alkyl or
C.sub.1-C.sub.6-alkoxy.
[0064] Examples of preferred diphenols of the formula are
hydroquinone, resorcinol, 4,4'-di-hydroxybiphenyl,
2,2-bis(4-hydroxyphenyl)propane,
2,4-bis(4-hydroxyphenyl)-2-methylbutane and
1,1-bis(4-hydroxyphenyl)cyclohexane. Particular preference is given
to 2,2-bis(4-hydroxyphenyl)propane and
1,1-bis(4-hydroxyphenyl)cyclohexane, and also to
1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
[0065] Either homopolycarbonates or copolycarbonates are suitable
as component A, and preference is given to the copolycarbonates of
bisphenol A, as well as to bisphenol A homopolymer.
[0066] Suitable polycarbonates may be branched in a known manner,
specifically by incorporating from 0.05 to 2.0 mol %, based on the
total of the diphenols used, of at least trifunctional compounds,
for example those having three or more phenolic OH groups.
[0067] Polycarbonates which have proven particularly suitable have
relative viscosities .eta..sub.rel of from 1.10 to 1.50, in
particular from 1.25 to 1.40. This corresponds to an average molar
mass M.sub.w (weight-average) of from 10 000 to 200 000 g/mol,
preferably from 20 000 to 80 000 g/mol.
[0068] The diphenols of the general formula are known per se or can
be prepared by known processes.
[0069] The polycarbonates may, for example, be prepared by reacting
the diphenols with phosgene in the interfacial process, or with
phosgene in the homogeneous-phase process (known as the pyridine
process), and in each case the desired molecular weight may be
achieved in a known manner by using an appropriate amount of known
chain terminators. (In relation to polydiorganosiloxane-containing
polycarbonates see, for example, DE-A 33 34 782.)
[0070] Examples of suitable chain terminators are phenol,
p-tert-butylphenol, or else long-chain alkylphenols, such as
4-(1,3-tetramethylbutyl)phenol as in DE-A 28 42 005, or
monoalkylphenols, or dialkylphenols with a total of from 8 to 20
carbon atoms in the alkyl substituents as in DE-A-35 06 472, such
as p-nonylphenol, 3,5-di-tert-butylphenol, p-tert-octylphenol,
p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol and
4-(3,5-dimethylheptyl)phenol.
[0071] For the purposes of the present invention, halogen-free
polycarbonates are polycarbonates composed of halogen-free
diphenols, of halogen-free chain terminators and, if used,
halogen-free branching agents, where the content of subordinate
amounts at the ppm level of hydrolyzable chlorine, resulting, for
example, from the preparation of the polycarbonates with phosgene
in the interfacial process, is not regarded as meriting the term
halogen-containing for the purposes of the invention.
Polycarbonates of this type with contents of hydrolyzable chlorine
at the ppm level are halogen-free polycarbonates for the purposes
of the present invention.
[0072] Other suitable components A) which may be mentioned are
amorphous polyester carbonates, where during the preparation
process phosgene has been replaced by aromatic dicarboxylic acid
units, such as isophthalic acid and/or terephthalic acid units.
Reference may be made at this point to EP-A 711 810 for further
details.
[0073] EP-A 365 916 describes other suitable copolycarbonates
having cycloalkyl radicals as monomer units.
[0074] It is also possible for bisphenol A to be replaced by
bisphenol TMC. Polycarbonates of this type are obtainable from
Bayer with the trademark APEC HT.RTM..
[0075] The inventive molding compositions comprise, as component
B), from 0.01 to 50% by weight, preferably from 0.5 to 20% by
weight, and in particular from 0.7 to 10% by weight, of B1) from at
least one highly branched or hyperbranched polycarbonate,
preferably with an OH number of below 1 to 600 mg KOH/g of
polycarbonate, with preference from 10 to 550 mg KOH/g of
polycarbonate, and in particular from 50 to 550 mg KOH/g of
polycarbonate (to DIN 53240, Part 2), or of at least one
hyperbranched polyester as component B2), or a mixture of these, as
explained above.
[0076] For the purposes of this invention, hyperbranched
polycarbonates B1) are non-crosslinked macromolecules having
hydroxy groups and carbonate groups, these having both structural
and molecular non-uniformity. Their structure may firstly be based
on a central molecule in the same way as dendrimers, but with
non-uniform chain length of the branches. Secondly, they may also
have a linear structure with functional pendant groups, or else
they may combine the two extremes, having linear and branched
molecular portions. See also P. J. Flory, J. Am. Chem. Soc. 1952,
74, 2718, and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499
for the definition of dendrimeric and hyperbranched polymers.
[0077] "Hyperbranched" in the context of the present invention
means that the degree of branching (DB), i.e. the average number of
dendritic linkages plus the average number of end groups per
molecule, is from 10 to 99.9%, preferably from 20 to 99%,
particularly preferably from 20 to 95%.
[0078] "Dendrimeric" in the context of the present invention means
that the degree of branching is from 99.9 to 100%. See H. Frey et
al., Acta Polym. 1997, 48, 30 for the definition of "degree of
branching".
[0079] The DB (degree of branching) of the relevant substrates is
defined as
DB = T + Z T + Z + L .times. 100 % , ##EQU00001##
(where T is the average number of terminal monomer units, Z is the
average number of branched monomer units, and L is the average
number of linear monomer units in the macromolecules of the
respective substances).
[0080] Component B1) preferably has a number-average molar mass
M.sub.n of from 100 to 15 000 g/mol, preferably from 200 to 12 000
g/mol, and in particular from 500 to 10 000 g/mol (GPC, PMMA
standard).
[0081] The glass transition temperature Tg is in particular from
-80 to +140.degree. C., preferably from -60 to 120.degree. C.
(according to DSC, DIN 53765).
[0082] In particular, the viscosity (mpas) at 23.degree. C. (to DIN
53019) is from 50 to 200 000, in particular from 100 to 150 000,
and very particularly preferably from 200 to 100 000.
[0083] Component B1) is preferably obtainable via a process which
comprises at least the following steps: [0084] a) reaction of at
least one organic carbonate (A) of the general formula
RO[(CO)].sub.nOR with at least one aliphatic, aliphatic/aromatic or
aromatic alcohol (B) which has at least 3 OH groups, with
elimination of alcohols ROH to give one or more condensates (K),
where each R, independently of the others, is a straight-chain or
branched aliphatic, aromatic/aliphatic or aromatic hydrocarbon
radical having from 1 to 20 carbon atoms, and where the radicals R
may also have bonding to one another to form a ring, and n is a
whole number from 1 to 5, or [0085] ab) reaction of phosgene,
diphosgene, or triphosgene with abovementioned alcohol (B), with
elimination of hydrogen chloride, and [0086] b) intermolecular
reaction of the condensates (K) to give a highly functional, highly
branched, or highly functional, hyperbranched polycarbonate, where
the quantitative proportion of the OH groups to the carbonates in
the reaction mixture is selected in such a way that the condensates
(K) have an average of either one carbonate group and more than one
OH group or one OH group and more than one carbonate group.
[0087] Phosgene, diphosgene, or triphosgene may be used as starting
material, but preference is given to organic carbonates.
[0088] Each of the radicals R of the organic carbonates (A) used as
starting material and having the general formula RO(CO).sub.nOR is,
independently of the others, a straight-chain or branched
aliphatic, aromatic/aliphatic or aromatic hydrocarbon radical
having from 1 to 20 carbon atoms. The two radicals R may also have
bonding to one another to form a ring. The radical is preferably an
aliphatic hydrocarbon radical, and particularly preferably a
straight-chain or branched alkyl radical having from 1 to 5 carbon
atoms, or a substituted or unsubstituted phenyl radical.
[0089] In particular, use is made of simple carbonates of the
formula RO(CO).sub.nOR; n is preferably from 1 to 3, in particular
1.
[0090] By way of example, dialkyl or diaryl carbonates may be
prepared from the reaction of aliphatic, araliphatic, or aromatic
alcohols, preferably monoalcohols, with phosgene. They may also be
prepared by way of oxidative carbonylation of the alcohols or
phenols by means of CO in the presence of noble metals, oxygen, or
NO.sub.x. In relation to preparation methods for diaryl or dialkyl
carbonates, see also "Ullmann's Encyclopedia of Industrial
Chemistry", 6th edition, 2000 Electronic Release, Verlag
Wiley-VCH,
[0091] Examples of suitable carbonates comprise aliphatic,
aromatic/aliphatic or aromatic carbonates, such as ethylene
carbonate, propylene 1,2- or 1,3-carbonate, diphenyl carbonate,
ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethyl
phenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl
carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl
carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl
carbonate, diheptyl carbonate, dioctyl carbonate, didecyl
carbonate, or didodecyl carbonate.
[0092] Examples of carbonates where n is greater than 1 comprise
dialkyl dicarbonates, such as di(tert-butyl) dicarbonate, or
dialkyl tricarbonates, such as di(tert-butyl) tricarbonate.
[0093] It is preferable to use aliphatic carbonates, in particular
those in which the radicals comprise from 1 to 5 carbon atoms, e.g.
dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl
carbonate, or diisobutyl carbonate.
[0094] The organic carbonates are reacted with at least one
aliphatic alcohol (B) which has at least 3 OH groups, or with
mixtures of two or more different alcohols.
[0095] Examples of compounds having at least three OH groups
comprise glycerol, trimethylolmethane, trimethylolethane,
trimethylol propane, 1,2,4-butanetriol, tris(hydroxymethyl)amine,
tris(hydroxyethyl)amine, tris(hydroxypropyl)amine, pentaerythritol,
diglycerol, triglycerol, polyglycerols, bis(trimethylolpropane),
tris(hydroxymethyl) isocyanurate, tris(hydroxyethyl) isocyanurate,
phloroglucinol, trihydroxytoluene, trihydroxydimethylbenzene,
phloroglucides, hexahydroxybenzene, 1,3,5-benzenetrimethanol,
1,1,1-tris(4'-hydroxyphenyl)methane,
1,1,1-tris(4'-hydroxyphenyl)ethane, or sugars, e.g. glucose,
trihydric or higher polyhydric polyetherols based on trihydric or
higher polyhydric alcohols and ethylene oxide, propylene oxide, or
butylene oxide, or polyesterols. Particular preference is given
here to glycerol, trimethylolethane, trimethylolpropane,
1,2,4-butanetriol, pentaerythritol, and also their polyetherols
based on ethylene oxide or propylene oxide.
[0096] These polyhydric alcohols may also be used in a mixture with
dihydric alcohols (B'), with the proviso that the average total OH
functionality of all of the alcohols used is greater than 2.
Examples of suitable compounds having two OH groups comprise
ethylene glycol, diethylene glycol, triethylene glycol, 1,2- and
1,3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl
glycol, 1,2-, 1,3-, and 1,4-butanediol, 1,2-, 1,3-, and
1,5-pentanediol, hexanediol, cyclopentanediol, cyclohexanediol,
cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane,
bis(4-hydroxycyclohexyl)ethane,
2,2-bis(4-hydroxycyclohexyl)propane,
1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, resorcinol,
hydroquinone, 4,4'-dihydroxyphenyl,
bis(4-bis(hydroxyphenyl)sulfide, bis(4-hydroxyphenyl) sulfone,
bis(hydroxymethyl)benzene, bis(hydroxymethyl)toluene,
bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)ethane,
2,2-bis(p-hydroxyphenyl)propane,
1,1-bis(p-hydroxyphenyl)cyclohexane, dihydroxybenzophenone,
dihydric polyether polyols based on ethylene oxide, propylene
oxide, butylene oxide, or mixtures of these, polytetrahydrofuran,
polycaprolactone, or polyesterols based on diols and dicarboxylic
acids.
[0097] The diols serve for fine adjustment of the properties of the
polycarbonate. If use is made of dihydric alcohols, the ratio of
dihydric alcohols B)', to the at least trihydric alcohols (B) is
set by the person skilled in the art and depends on the desired
properties of the polycarbonate. The amount of the alcohol(s) (B')
is generally from 0 to 50 mol %, based on the total amount of all
of the alcohols (B) and (B') taken together. The amount is
preferably from 0 to 45 mol %, particularly preferably from 0 to 35
mol %, and very particularly preferably from 0 to 30 mol %.
[0098] The reaction of phosgene, diphosgene, or triphosgene with
the alcohol or alcohol mixture generally takes place with
elimination of hydrogen chloride, and the reaction of the
carbonates with the alcohol or alcohol mixture to give the
inventive highly functional highly branched polycarbonate takes
place with elimination of the monofunctional alcohol or phenol from
the carbonate molecule.
[0099] The highly functional highly branched polycarbonates formed
by the inventive process have termination by hydroxy groups and/or
by carbonate groups after the reaction, i.e. with no further
modification. They have good solubility in various solvents, e.g.
in water, alcohols, such as methanol, ethanol, butanol,
alcohol/water mixtures, acetone, 2-butanone, ethyl acetate, butyl
acetate, methoxypropyl acetate, methoxyethyl acetate,
tetrahydrofuran, dimethylformamide, dimethylacetamide,
N-methylpyrrolidone, ethylene carbonate, or propylene
carbonate.
[0100] For the purposes of this invention, a highly functional
polycarbonate is a product which, besides the carbonate groups
which form the polymer skeleton, further has at least three,
preferably at least six, more preferably at least ten, terminal or
pendant functional groups. The functional groups are carbonate
groups and/or OH groups. There is in principle no upper restriction
on the number of the terminal or pendant functional groups, but
products having a very high number of functional groups can have
undesired properties, such as high viscosity or poor solubility.
The highly functional polycarbonates of the present invention
mostly have not more than 500 terminal or pendant functional
groups, preferably not more than 100 terminal or pendant functional
groups.
[0101] When preparing the highly functional polycarbonates B1), it
is necessary to adjust the ratio of the compounds comprising OH
groups to phosgene or carbonate in such a way that the simplest
resultant condensate (hereinafter termed condensate (K)) comprises
an average of either one carbonate group or carbamoyl group and
more than one OH group or one OH group and more than one carbonate
group or carbamoyl group. The simplest structure of the condensate
(K) composed of a carbonate (A) and a di- or polyalcohol (B) here
results in the arrangement XY.sub.n or Y.sub.nX, where X is a
carbonate group, Y is a hydroxy group, and n is generally a number
from 1 to 6, preferably from 1 to 4, particularly preferably from 1
to 3. The reactive group which is the single resultant group here
is generally termed "focal group" below.
[0102] By way of example, if during the preparation of the simplest
condensate (K) from a carbonate and a dihydric alcohol the reaction
ratio is 1:1, the average result is a molecule of XY type,
illustrated by the general formula 1.
##STR00003##
[0103] During the preparation of the condensate (K) from a
carbonate and a trihydric alcohol with a reaction ratio of 1:1, the
average result is a molecule of XY.sub.2 type, illustrated by the
general formula 2. A carbonate group is focal group here.
##STR00004##
[0104] During the preparation of the condensate (K) from a
carbonate and a tetrahydric alcohol, likewise with the reaction
ratio 1:1, the average result is a molecule of XY.sub.3 type,
illustrated by the general formula 3. A carbonate group is focal
group here.
##STR00005##
[0105] R in the formulae 1-3 has the definition given at the
outset, and R.sup.1 is an aliphatic or aromatic radical.
[0106] The condensate (K) may, by way of example, also be prepared
from a carbonate and a trihydric alcohol, as illustrated by the
general formula 4, the molar reaction ratio being 2:1. Here, the
average result is a molecule of X.sub.2Y type, an OH group being
focal group here. In formula 4, R and R.sup.1 are as defined in
formulae 1-3.
##STR00006##
[0107] If difunctional compounds, e.g. a dicarbonate or a diol, are
also added to the components, this extends the chains, as
illustrated by way of example in the general formula 5. The average
result is again a molecule Of XY.sub.2 type, a carbonate group
being focal group.
##STR00007##
[0108] In formula 5, R.sup.2 is an organic, preferably aliphatic
radical, and R and R.sup.1 are as defined above.
[0109] It is also possible to use two or more condensates (K) for
the synthesis. Here, firstly two or more alcohols or two or more
carbonates may be used. Furthermore, mixtures of various
condensates of different structure can be obtained via the
selection of the ratio of the alcohols used and of the carbonates
or the phosgenes. This may be illustrated taking the example of the
reaction of a carbonate with a trihydric alcohol. If the starting
products are reacted in a ratio of 1:1, as shown in (II), the
result is an XY.sub.2 molecule. If the starting products are
reacted in a ratio of 2:1, as shown in (IV), the result is an
X.sub.2Y molecule. If the ratio is from 1:1 to 2:1, the result is a
mixture of XY.sub.2 and X.sub.2Y molecules.
[0110] According to the invention, the simple condensates (K)
described by way of example in the formulae 1-5 preferentially
react intermolecularly to form highly functional polycondensates,
hereinafter termed polycondensates (P). The reaction to give the
condensate (K) and to give the polycondensate (P) usually takes
place at a temperature of from 0 to 250.degree. C., preferably from
60 to 160.degree. C., in bulk or in solution. Use may generally be
made here of any of the solvents which are inert with respect to
the respective starting materials. Preference is given to use of
organic solvents, e.g. decane, dodecane, benzene, toluene,
chlorobenzene, xylene, dimethylformamide, dimethylacetamide, or
solvent naphtha.
[0111] In one preferred embodiment, the condensation reaction is
carried out in bulk. To accelerate the reaction, the phenol or the
monohydric alcohol ROH liberated during the reaction can be removed
by distillation from the reaction equilibrium if appropriate at
reduced pressure.
[0112] If removal by distillation is intended, it is generally
advisable to use those carbonates which liberate alcohols ROH with
a boiling point below 140.degree. C. during the reaction.
[0113] Catalysts or catalyst mixtures may also be added to
accelerate the reaction. Suitable catalysts are compounds which
catalyze esterification or transesterification reactions, e.g.
alkali metal hydroxides, alkali metal carbonates, alkali metal
hydrogencarbonates, preferably of sodium, of potassium, or of
cesium, tertiary amines, guanidines, ammonium compounds,
phosphonium compounds, organoaluminum, organotin, organozinc,
organotitanium, organozirconium, or organobismuth compounds, or
else what are known as double metal cyanide (DMC) catalysts, e.g.
as described in DE 10138216 or DE 10147712.
[0114] It is preferable to use potassium hydroxide, potassium
carbonate, potassium hydrogencarbonate, diazabicyclooctane (DABCO),
diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles,
such as imidazole, 1-methylimidazole, or 1,2-dimethylimidazole,
titanium tetrabutoxide, titanium tetraisopropoxide, dibutyltin
oxide, dibutyltin dilaurate, stannous dioctoate, zirconium
acetylacetonate, or mixtures thereof.
[0115] The amount of catalyst generally added is from 50 to 10 000
ppm by weight, preferably from 100 to 5000 ppm by weight, based on
the amount of the alcohol mixture or alcohol used.
[0116] It is also possible to control the intermolecular
polycondensation reaction via addition of the suitable catalyst or
else via selection of a suitable temperature. The average molecular
weight of the polymer (P) may moreover be adjusted by way of the
composition of the starting components and by way of the residence
time.
[0117] The condensates (K) and the polycondensates (P) prepared at
an elevated temperature are usually stable at room temperature for
a relatively long period.
[0118] The nature of the condensates (K) permits polycondensates
(P) with different structures to result from the condensation
reaction, these having branching but no crosslinking. Furthermore,
in the ideal case, the polycondensates (P) have either one
carbonate group as focal group and more than two OH groups or else
one OH group as focal group and more than two carbonate groups. The
number of the reactive groups here is the result of the nature of
the condensates (K) used and the degree of polycondensation.
[0119] By way of example, a condensate (K) according to the general
formula 2 can react via triple intermolecular condensation to give
two different polycondensates (P), represented in the general
formulae 6 and 7.
##STR00008##
[0120] In formula 6 and 7, R and R.sup.1 are as defined above.
[0121] There are various ways of terminating the intermolecular
polycondensation reaction. By way of example, the temperature may
be lowered to a range where the reaction stops and the product (K)
or the polycondensate (P) is storage-stable.
[0122] It is also possible to deactivate the catalyst, for example
in the case of basic catalysts via addition of Lewis acids or
proton acids.
[0123] In another embodiment, as soon as the intermolecular
reaction of the condensate (K) has produced a polycondensate (P)
with the desired degree of polycondensation, a product having
groups reactive toward the focal group of (P) may be added to the
product (P) to terminate the reaction. In the case of a carbonate
group as focal group, by way of example, a mono-, di-, or polyamine
may be added. In the case of a hydroxy group as focal group, by way
of example, a mono-, di-, or polyisocyanate, or a compound
comprising epoxy groups, or an acid derivative which reacts with OH
groups, can be added to the product (P).
[0124] The inventive highly functional polycarbonates are mostly
prepared in the pressure range from 0.1 mbar to 20 bar, preferably
at from 1 mbar to 5 bar, in reactors or reaction cascades which are
operated batchwise, semicontinuously, or continuously.
[0125] The inventive products can be further processed without
further purification after their preparation by virtue of the
abovementioned adjustment of the reaction conditions and, if
appropriate, by virtue of the selection of the suitable
solvent.
[0126] In another preferred embodiment, the product is stripped,
i.e. freed from low-molecular-weight, volatile compounds. For this,
once the desired degree of conversion has been reached the catalyst
may optionally be deactivated and the low-molecular-weight volatile
constituents, e.g. monoalcohols, phenols, carbonates, hydrogen
chloride, or volatile oligomeric or cyclic compounds, can be
removed by distillation, if appropriate with introduction of a gas,
preferably nitrogen, carbon dioxide, or air, if appropriate at
reduced pressure.
[0127] In another preferred embodiment, the inventive
polycarbonates may comprise other functional groups besides the
functional groups present at this stage by virtue of the reaction.
The functionalization may take place during the process to increase
molecular weight, or else subsequently, i.e. after completion of
the actual polycondensation.
[0128] If, prior to or during the process to increase molecular
weight, components are added which have other functional groups or
functional elements besides hydroxy or carbonate groups, the result
is a polycarbonate polymer with randomly distributed
functionalities other than the carbonate or hydroxy groups.
[0129] Effects of this type can, by way of example, be achieved via
addition, during the polycondensation, of compounds which bear
other functional groups or functional elements, such as mercapto
groups, primary, secondary or tertiary amino groups, ether groups,
derivatives of carboxylic acids, derivatives of sulfonic acids,
derivatives of phosphonic acids, silane groups, siloxane groups,
aryl radicals, or long-chain alkyl radicals, besides hydroxy
groups, carbonate groups or carbamoyl groups. Examples of compounds
which may be used for modification by means of carbamate groups are
ethanolamine, propanolamine, isopropanolamine,
2-(butylamino)ethanol, 2-(cyclohexylamino)ethanol,
2-amino-1-butanol, 2-(2'-aminoethoxy)ethanol or higher alkoxylation
products of ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine,
diethanolamine, dipropanolamine, diisopropanolamine,
tris(hydroxymethyl)aminomethane, tris(hydroxyethyl)aminomethane,
ethylenediamine, propylenediamine, hexamethylenediamine or
isophoronediamine.
[0130] An example of a compound which can be used for modification
with mercapto groups is mercaptoethanol. By way of example,
tertiary amino groups can be produced via incorporation of
N-methyldiethanolamine, N-methyldipropanolamine or
N,N-dimethylethanolamine. By way of example, ether groups may be
generated via co-condensation of dihydric or higher polyhydric
polyetherols. Long-chain alkyl radicals can be introduced via
reaction with long-chain alkanediols, and reaction with alkyl or
aryl diisocyanates generates polycarbonates having alkyl, aryl, and
urethane groups, or urea groups.
[0131] Ester groups can be produced via addition of dicarboxylic
acids, tricarboxylic acids, or, for example, dimethyl terephalate,
or tricarboxylic esters.
[0132] Subsequent functionalization can be achieved by using an
additional step of the process (step c)) to react the resultant
highly functional highly branched, or highly functional
hyperbranched polycarbonate with a suitable functionalizing reagent
which can react with the OH and/or carbonate groups or carbamoyl
groups of the polycarbonate.
[0133] By way of example, highly functional highly branched, or
highly functional hyperbranched polycarbonates comprising hydroxy
groups can be modified via addition of molecules comprising acid
groups or isocyanate groups. By way of example, polycarbonates
comprising acid groups can be obtained via reaction with compounds
comprising anhydride groups.
[0134] Highly functional polycarbonates comprising hydroxy groups
may moreover also be converted into highly functional polycarbonate
polyether polyols via reaction with alkylene oxides, e.g. ethylene
oxide, propylene oxide, or butylene oxide.
[0135] A great advantage of the process is its cost-effectiveness.
Both the reaction to give a condensate (K) or polycondensate (P)
and also the reaction of (K) or (P) to give polycarbonates with
other functional groups or elements can take place in one reactor,
this being advantageous technically and in terms of
cost-effectiveness.
[0136] The inventive molding compositions may comprise, as
component B2), at least one hyperbranched polyester of
A.sub.xB.sub.y type, where [0137] x is at least 1.1, preferably at
least 1.3, in particular at least 2 [0138] y is at least 2.1,
preferably at least 2.5, in particular at least 3.
[0139] Use may also be made of mixtures as units A and/or B, of
course.
[0140] An A.sub.xB.sub.y-type polyester is a condensate composed of
an x-functional molecule A and a y-functional molecule B. By way of
example, mention may be made of a polyester composed of adipic acid
as molecule A (x=2) and glycerol as molecule B (y=3).
[0141] For the purposes of this invention, hyperbranched polyesters
B2) are non-crosslinked macromolecules having hydroxy groups and
carbonate groups, these having both structural and molecular
non-uniformity Their structure may firstly be based on a central
molecule in the same way as dendrimers, but with non-uniform chain
length of the branches. Secondly, they may also have a linear
structure with functional pendant groups, or else they may combine
the two extremes, having linear and branched molecular portions.
See also P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718, and H. Frey
et al., Chem. Eur. J. 2000, 6, no. 14, 2499 for the definition of
dendrimeric and hyperbranched polymers.
[0142] "Hyperbranched" in the context of the present invention
means that the degree of branching (DB), i.e. the average number of
dendritic linkages plus the average number of end groups per
molecule, is from 10 to 99.9%, preferably from 20 to 99%,
particularly preferably from 20 to 95%. "Dendrimer" in the context
of the present invention means that the degree of branching is from
99.9 to 100%. See H. Frey et al., Acta Polym. 1997, 48, 30 and
formula cited above under B1) for the definition of "degree of
branching".
[0143] Component B2) preferably has an M.sub.n of from 300 to 30
000 g/mol, in particular from 400 to 25 000 g/mol, and very
particularly from 500 to 20 000 g/mol, determined by means of GPC,
PMMA standard, dimethylacetamide eluent.
[0144] B2) preferably has an OH number of from 0 to 600 mg KOH/g of
polyester, preferably of from 1 to 500 mg KOH/g of polyester, in
particular from 20 to 500 mg KOH/g of polyester to DIN 53240, and
preferably a COOH number of from 0 to 600 mg KOH/g of polyester,
preferably from 1 to 500 mg KOH/g of polyester, and in particular
from 2 to 500 mg KOH/g of polyester.
[0145] The T.sub.g is preferably from -50.degree. C. to 140.degree.
C., and in particular from -50 to 100.degree. C. (by means of DSC,
to DIN 53765).
[0146] Preference is particularly given to those components B2) in
which at least one OH or COOH number is greater than 0, preferably
greater than 0.1, and in particular greater than 0.5.
[0147] The inventive component B2) is in particular obtainable via
the processes described below, specifically by reacting [0148] (a)
one or more dicarboxylic acids or one or more derivatives of the
same with one or more at least trihydric alcohols or [0149] (b) one
or more tricarboxylic acids or higher polycarboxylic acids or one
or more derivatives of the same with one or more diols in the
presence of a solvent and optionally in the presence of an
inorganic, organometallic, or low-molecular-weight organic
catalyst, or of an enzyme. The reaction in solvent is the preferred
preparation method.
[0150] For the purposes of the present invention, highly functional
hyperbranched polyesters B2) have molecular and structural
non-uniformity. Their molecular non-uniformity distinguishes them
from dendrimers, and they can therefore be prepared at considerably
lower cost.
[0151] Among the dicarboxylic acids which can be reacted according
to variant (a) are, by way of example, oxalic acid, malonic acid,
succnic acid, glutaric acid, adipic acid, pimelic acid, suberic
acid, azelaic acid, sebacic acid,
undecane-.alpha.,.omega.-dicarboxylic acid,
dodecane-.alpha.,.omega.-dicarboxylic acid, cis- and
trans-cyclohexane-1,2-dicarboxylic acid, cis- and
trans-cyclohexane-1,3-dicarboxylic acid, cis- and
trans-cyclohexane-1,4-di-carboxylic acid, cis- and
trans-cyclopentane-1,2-dicarboxylic acid, and cis- and
trans-cyclopentane-1,3-dicarboxylic acid,
and the abovementioned dicarboxylic acids may have substitution by
one or more radicals selected from [0152] C.sub.1-C.sub.10-alkyl
groups, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl,
neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl,
sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl, and
n-decyl, [0153] C.sub.3-C.sub.12-cyCloalkyl groups, such as
cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl;
preference is given to cyclopentyl, cyclohexyl, and cycloheptyl;
[0154] alkylene groups, such as methylene or ethylidene, or [0155]
C.sub.6-C.sub.14-aryl groups, such as phenyl, 1-naphthyl,
2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl,
2-phenanthryl, 3-phenanthryl, 4-phenanthryl, and 9-phenanthryl,
preferably phenyl, 1-naphthyl, and 2-naphthyl, particularly
preferably phenyl.
[0156] Examples which may be mentioned as representatives of
substituted dicarboxylic acids are: 2-methylmalonic acid,
2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid,
2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid,
3,3-dimethylglutaric acid.
[0157] Among the dicarboxylic acids which can be reacted according
to variant (a) are also ethylenically unsaturated acids, such as
maleic acid and fumaric acid, and aromatic dicarboxylic acids, such
as phthalic acid, isophthalic acid or terephthalic acid.
[0158] It is also possible to use mixtures of two or more of the
abovementioned representative compounds.
[0159] The dicarboxylic acids may either be used as they stand or
be used in the form of derivatives.
[0160] Derivatives are preferably [0161] the relevant anhydrides in
monomeric or else polymeric form, [0162] mono- or dialkyl esters,
preferably mono- or dimethyl esters, or the corresponding mono- or
diethyl esters, or else the mono- and dialkyl esters derived from
higher alcohols, such as n-propanol.sub.1 isopropanol, n-butanol,
isobutanol, tert-butanol, n-pentanol, n-hexanol, [0163] and also
mono- and divinyl esters, and [0164] mixed esters, preferably
methyl ethyl esters.
[0165] In the preferred preparation process it is also possible to
use a mixture composed of a dicarboxylic acid and one or more of
its derivatives. Equally, it is possible to use a mixture of two or
more different derivatives of one or more dicarboxylic acids.
[0166] It is particularly preferable to use succinic acid, glutaric
acid, adipic acid, phthalic acid, isophthalic acid, terephthalic
acid, or the mono- or dimethyl esters thereof. It is very
particularly preferable to use adipic acid.
[0167] Examples of at least trihydric alcohols which may be reacted
are: glycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol,
n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol,
n-hexane-1,3,6-triol, trimethylolbutane, trimethylolpropane or
ditrimethylolpropane, trimethylolethane, pentaerythritol or
dipentaerythritol; sugar alcohols, such as mesoerythritol,
threitol, sorbitol, mannitol, or mixtures of the above at least
trihydric alcohols. It is preferable to use glycerol,
trimethylolpropane, trimethylolethane, and pentaerythritol.
[0168] Examples of tricarboxylic acids or polycarboxylic acids
which can be reacted according to variant (b) are
benzene-1,2,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid,
benzene-1,2,4,5-tetracarboxylic acid, and mellitic acid.
[0169] Tricarboxylic acids or polycarboxylic acids may be used in
the inventive reaction either as they stand or else in the form of
derivatives.
[0170] Derivatives are preferably [0171] the relevant anhydrides in
monomeric or else polymeric form, [0172] mono-, di-, or trialkyl
esters, preferably mono-, di-, or trimethyl esters, or the
corresponding mono-, di-, or triethyl esters, or else the mono-,
di-, and triesters derived from higher alcohols, such as
n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol,
n-pentanol, n-hexanol, or else mono-, di-, or trivinyl esters
[0173] and mixed methyl ethyl esters.
[0174] For the purposes of the present invention, it is also
possible to use a mixture composed of a tri- or polycarboxylic acid
and one or more of its derivatives. For the purposes of the present
invention it is likewise possible to use a mixture of two or more
different derivatives of one or more tri- or polycarboxylic acids,
in order to obtain component B2).
[0175] Examples of diols used for variant (b) of the present
invention are ethylene glycol, propane-1,2-diol, propane-1,3-diol,
butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3-diol,
pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol,
pentane-1,5-diol, pentane-2,3-diol, pentane-2,4-diol,
hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol,
hexane-1,6-diol, hexane-2,5-diol, heptan-1,2-diol, 1,7-heptanediol,
1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol,
1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol,
1,5-hexadiene-3,4-diol, cyclopentanediols, cyclohexanediols,
inositol and derivatives, (2)-methylpentane-2,4-diol,
2,4-dimethylpentane-2,4-diol, 2-ethylhexane-1,3-diol,
2,5-dimethylhexane-2,5-diol, 2,2,4-trimethylpentane-1,3-diol,
pinacol, diethylene glycol, triethylene glycol, dipropylene glycol,
tripropylene glycol, polyethylene glycols
HO(CH.sub.2CH.sub.2O).sub.n--H or polypropylene glycols
HO(CH[CH.sub.3]CH.sub.2O).sub.n--H or mixtures of two or more
representative compounds of the above compounds, where n is a whole
number and n=4. One, or else both, hydroxy groups here in the
abovementioned diols may also be replaced by SH groups. Preference
is given to ethylene glycol, propane-1,2-diol, and diethylene
glycol, triethylene glycol, dipropylene glycol, and tripropylene
glycol.
[0176] The molar ratio of the molecules A to molecules B in the
A.sub.xB.sub.y polyester in the variants (a) and (b) is from 4:1 to
1:4, in particular from 2:1 to 1:2.
[0177] The at least trihydric alcohols reacted according to variant
(a) of the process may have hydroxy groups of which all have
identical reactivity. Preference is also given here to at least
trihydric alcohols whose OH groups initially have identical
reactivity, but where reaction with at least one acid group can
induce a fall-off in reactivity of the remaining OH groups as a
result of steric or electronic effects. By way of example, this
applies when trimethylolpropane or pentaerythritol is used.
[0178] However, the at least trihydric alcohols reacted according
to variant (a) may also have hydroxy groups having at least two
different chemical reactivities.
[0179] The different reactivity of the functional groups here may
derive either from chemical causes (e.g. primary/secondary/tertiary
OH group) or from steric causes.
[0180] By way of example, the triol may comprise a triol which has
primary and secondary hydroxy groups, a preferred example being
glycerol.
[0181] When the inventive reaction is carried out according to
variant (a), the triol or the mixture of at least trihydric
alcohols may also have been mixed with dihydric alcohols,
preferably up to 50 mol %, based on the entire alcohol mixture, but
it is preferable to operate in the absence of diols and of
monohydric alcohols.
[0182] When the inventive reaction is carried out according to
variant (b), the tricarboxylic acid or the mixture of at least
tribasic carboxylic acids may also have been mixed with dibasic
carboxylic acids, preferably up to 50 mol %, based on the entire
acid mixture, but it is preferable to operate in the absence of
mono- or dicarboxylic acids.
[0183] The inventive process is carried out in the presence of a
solvent. By way of example, hydrocarbons are suitable, such as
paraffins or aromatics. Particularly suitable paraffins are
n-heptan and cyclohexane. Particularly suitable aromatics are
toluene, ortho-xylene, meta-xylene, para-xylene, xylene in the form
of an isomer mixture, ethylbenzene, chlorobenzene, and ortho- and
meta-dichlorobenzene. Other solvents very particularly suitable in
the absence of acidic catalysts are: ethers, such as dioxane or
tetrahydrofuran, and ketones, such as methyl ethyl ketone and
methyl isobutyl ketone.
[0184] According to the invention, the amount of solvent added is
at least 0.1% by weight, based on the weight of the starting
materials used and to be reacted, preferably at least 1% by weight,
and particularly preferably at least 10% by weight. It is also
possible to use excesses of solvent, based on the weight of
starting materials used and to be reacted, e.g. from 1.01 to 10
times the amount. Solvent amounts of more than 100 times the weight
of the starting materials used and to be reacted are not
advantageous, because the reaction rate decreases markedly at
markedly lower concentrations of the reactants, giving
uneconomically long reaction times.
[0185] To carry out the process preferred according to the
invention, operations may be carried out in the presence of a
dehydrating agent as additive, added at the start of the reaction.
Suitable examples are molecular sieves, in particular 4 .ANG.
molecular sieve, MgSO.sub.4, and Na.sub.2SO.sub.4. During the
reaction it is also possible to add further dehydrating agent or to
replace dehydrating agent by fresh dehydrating agent. During the
reaction it is also possible to remove the water or alcohol formed
by distillation and, for example, to use a water trap.
[0186] The reaction may be carried out in the absence of acidic
catalysts. It is preferable to operate in the presence of an acidic
inorganic, organometallic, or organic catalyst, or a mixture
composed of two or more acidic inorganic, organometallic, or
organic catalysts.
[0187] For the purposes of the present invention, examples of
acidic inorganic catalysts are sulfuric acid, phosphoric acid,
phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate,
alum, acidic silica gel (pH=6, in particular=5), and acidic
aluminum oxide. Examples of other compounds which can be used as
acidic inorganic catalysts are aluminum compounds of the general
formula Al(OR).sub.3 and titanates of the general formula
Tl(OR).sub.4, where each of the radicals R may be identical or
different and is selected independently of the others from [0188]
C.sub.1-C.sub.10-alkyl radicals, such as methyl, ethyl, n-propyl,
isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,
isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl,
n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl,
2-ethylhexyl, n-nonyl, and n-decyl, [0189]
C.sub.3-C.sub.12-cycloalkyl radicals, such as cyclopropyl,
cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
cyclononyl, cyclodecyl, cycloundecyl, and cyclododecyl; preference
is given to cyclopentyl, cyclohexyl, and cycloheptyl.
[0190] Each of the radicals R in Al(OR).sub.3 or Ti(OR).sub.4 is
preferably identical and selected from isopropyl or
2-ethylhexyl.
[0191] Examples of preferred acidic organometallic catalysts are
selected from dialkyltin oxides R.sub.2SnO, where R is defined as
above. A particularly preferred representative compound for acidic
organometallic catalysts is di-n-butyltin oxide, which is
commercially available as "oxo-tin", or di-n-butyltin
dilaurate.
[0192] Preferred acidic organic catalysts are acidic organic
compounds having, by way of example, phosphate groups, sulfonic
acid groups, sulfate groups, or phosphonic acid groups. Particular
preference is given to sulfonic acids, such as para-toluenesulfonic
acid. Acidic ion exchangers may also be used as acidic organic
catalysts, e.g. polystyrene resins comprising sulfonic acid groups
and crosslinked with about 2 mol % of divinylbenzene.
[0193] It is also possible to use combinations of two or more of
the abovementioned catalysts. It is also possible to use an
immobilized form of those organic or organometallic, or else
inorganic catalysts which take the form of discrete molecules.
[0194] If the intention is to use acidic inorganic, organometallic,
or organic catalysts, according to the invention the amount used is
from 0.1 to 10% by weight, preferably from 0.2 to 2% by weight, of
catalyst.
[0195] The inventive process is carried out under inert gas, e.g.
under carbon dioxide, nitrogen, or a noble gas, among which mention
may particularly be made of argon.
[0196] The inventive process is carried out at temperatures of from
60 to 200.degree. C. It is preferable to operate at temperatures of
from 130 to 180.degree. C., in particular up to 150.degree. C. or
below that temperature. Maximum temperatures up to 145.degree. C.
are particularly preferred, and temperatures up to 135.degree. C.
are very particularly preferred.
[0197] The pressure conditions for the inventive process are not
critical per se. It is possible to operate at markedly reduced
pressure, e.g. at from 10 to 500 mbar. The inventive process may
also be carried out at pressures above 500 mbar. A reaction at
atmospheric pressure is preferred for reasons of simplicity;
however, conduct at slightly increased pressure is also possible,
e.g. up to 1200 mbar. It is also possible to operate at markedly
increased pressure, e.g. at pressures up to 10 bar. Reaction at
atmospheric pressure is preferred.
[0198] The reaction time for the inventive process is usually from
10 minutes to 25 hours, preferably from 30 minutes to 10 hours, and
particularly preferably from one to 8 hours.
[0199] Once the reaction has ended, the highly functional
hyperbranched polyesters can easily be isolated, e.g. by removing
the catalyst by filtration and concentrating the mixture, the
concentration process here usually being carried out at reduced
pressure. Other work-up methods with good suitability are
precipitation after addition of water, followed by washing and
drying.
[0200] Component B2) can also be prepared in the presence of
enzymes or decomposition products of enzymes (according to DE-A 101
63163). For the purposes of the present invention, the term acidic
organic catalysts does not include the dicarboxylic acids reacted
according to the invention.
[0201] It is preferable to use lipases or esterases. Lipases and
esterases with good suitability are Candida cylindracea, Candida
lipolytica, Candida rugosa, Candida antarctica, Candida utilis,
Chromobacterium viscosum, Geotrichum viscosum, Geotrichum candidum,
Mucor javanicus, Mucor mihei, pig pancreas, pseudomonas spp.,
pseudomonas fluorescens, Pseudomonas cepacia, Rhizopus arrhizus,
Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus
niger, Penicillium roquefortii, Penicillium camembertii, or
esterase from Bacillus spp. and Bacillus thermoglucosidasius.
Candida antarctica lipase B is particularly preferred. The enzymes
listed are commercially available, for example from Novozymes
Biotech Inc., Denmark.
[0202] The enzyme is preferably used in immobilized form, for
example on silica gel or Lewatit.RTM.. The processes for
immobilizing enzymes are known per se, e.g. from Kurt Faber,
"Biotransformations in organic chemistry", 3rd edition 1997,
Springer Verlag, Chapter 3.2 "Immobilization" pp. 345-356.
Immobilized enzymes are commercially available, for example from
Novozymes Biotech Inc., Denmark.
[0203] The amount of immobilized enzyme used is from 0.1 to 20% by
weight, in particular from 10 to 15% by weight, based on the total
weight of the starting materials used and to be reacted.
[0204] The inventive process is carried out at temperatures above
60.degree. C. It is preferable to operate at temperatures of
100.degree. C. or below that temperature. Preference is given to
temperatures up to 80.degree. C., very particular preference is
given to temperatures of from 62 to 75.degree. C., and still more
preference is given to temperatures of from 65 to 75.degree. C.
[0205] The inventive process is carried out in the presence of a
solvent. Examples of suitable compounds are hydrocarbons, such as
paraffins or aromatics. Particularly suitable paraffins are
n-heptane and cyclohexane. Particularly suitable aromatics are
toluene, ortho-xylene, meta-xylene, para-xylene, xylene in the form
of an isomer mixture, ethylbenzene, chlorobenzene and ortho- and
meta-dichlorobenzene. Other very particularly suitable solvents
are: ethers, such as dioxane or tetrahydrofuran, and ketones, such
as methyl ethyl ketone and methyl isobutyl ketone.
[0206] The amount of solvent added is at least 5 parts by weight,
based on the weight of the starting materials used and to be
reacted, preferably at least 50 parts by weight, and particularly
preferably at least 100 parts by weight. Amounts of more than 10
000 parts by weight of solvent are undesirable, because the
reaction rate decreases markedly at markedly lower concentrations,
giving uneconomically long reaction times.
[0207] The inventive process is carried out at pressures above 500
mbar. Preference is given to the reaction at atmospheric pressure
or slightly increased pressure, for example at up to 1200 mbar. It
is also possible to operate under markedly increased pressure, for
example at pressures up to 10 bar. The reaction at atmospheric
pressure is preferred.
[0208] The reaction time for the inventive process is usually from
4 hours to 6 days, preferably from 5 hours to 5 days, and
particularly preferably from 8 hours to 4 days.
[0209] Once the reaction has ended, the highly functional
hyperbranched polyesters can be isolated, e.g. by removing the
enzyme by filtration and concentrating the mixture, this
concentration process usually being carried out at reduced
pressure. Other work-up methods with good suitability are
precipitation after addition of water, followed by washing and
drying.
[0210] The highly functional, hyperbranched polyesters obtainable
by the inventive process feature particularly low contents of
discolored and resinified material. For the definition of
hyperbranched polymers, see also: P. J. Flory, J. Am. Chem. Soc.
1952, 74, 2718, and A. Sunder et al., Chem. Eur. J. 2000, 6, no. 1,
1-8. However, in the context of the present invention, "highly
functional hyperbranched" means that the degree of branching, i.e.
the average number of dendritic linkages plus the average number of
end groups per molecule, is from 10 to 99.9%, preferably from 20 to
99%, particularly preferably from 30 to 90% (see in this connection
H. Frey et al. Acta Polym. 1997, 48, 30).
[0211] The inventive polyesters have a molar mass M.sub.w of from
500 to 50 000 g/mol, preferably from 1000 to 20 000 g/mol,
particularly preferably from 1000 to 19 000 g/mol. The
polydispersity is from 1.2 to 50, preferably from 1.4 to 40,
particularly preferably from 1.5 to 30, and very particularly
preferably from 1.5 to 10. They are usually very soluble, i.e.
clear solutions can be prepared using up to 50% by weight, in some
cases even up to 80% by weight, of the inventive polyesters in
tetrahydrofuran (THF), n-butyl acetate, ethanol, and numerous other
solvents, with no gel particles detectable by the naked eye.
[0212] The inventive highly functional hyperbranched polyesters are
carboxy-terminated, carboxy- and hydroxy-terminated, and preferably
hydroxy-terminated.
[0213] The ratios of the components B1) :B2) are preferably from
1:20 to 20:1, in particular from 1:15to 15:1, and very particularly
from 1.5 to 5:1 if a mixture of these is used.
[0214] The hyperbranched polycarbonates B1)/polyesters B2) used are
nanoparticles. The size of the particles in the compounded material
is from 20 to 500 nm, preferably from 50 to 300 nm.
[0215] Compounded materials of this type are available
commercially, e.g. in the form of Ultradur.RTM. high speed.
[0216] The inventive molding compositions comprise, as component
C), from 0.01 to 10% by weight, preferably from 0.5 to 7% by
weight, and in particular from 1 to 5% by weight, of epoxidized
naturally occurring oils or fatty acid esters, or a mixture of
these.
[0217] The epoxidized compounds preferably used as component C) are
those whose epoxy groups are non-terminal (epoxy groups which may
be called "internal" within the hydrocarbon chain).
[0218] The content of epoxy groups is preferably from 1 to 20% by
weight, with preference from 4 to 15% by weight, and in particular
from 6 to 12% by weight, based on the respective component C).
[0219] Preferred naturally occurring oils are olive oil, linseed
oil, palm oil, peanut oil, coconut oil, tung oil, rapeseed oil,
castor oil, cod liver oil, or a mixture of these, and particular
preference is given here to soybean oil.
[0220] The molecular weight of these oils is preferably from 500 to
1000, in particular from 600 to 900. These linseed or soybean oils
are mixtures of fatty acid triglycerides, with predominant C.sub.18
carboxylic acid fraction.
[0221] The epoxidized fatty acid esters can generally be prepared
from these naturally occurring oils by methods familiar to the
person skilled in the art.
[0222] Preference is given to use of esters of saturated or
unsaturated carboxylic acids having from 10 to 40, preferably from
16 to 22 carbon atoms with saturated aliphatic alcohols having from
2 to 40, preferably from 2 to 6, carbon atoms.
[0223] The carboxylic acids may be monobasic or dibasic, and
examples which may be mentioned are pelargonic acid, palmitic acid,
lauric acid, margaric acid, dodecanedioic acid, behenic acid, and
particularly preferably stearic acid, capric acid, and also
montanic acid (a mixture of fatty acids having from 30 to 40 carbon
atoms), linoleic acid, linolenic acid, and eleostearic acid, and
oleic acid.
[0224] The aliphatic alcohols may be mono- to tetrahydric. Examples
of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene
glycol, propylene glycol, neopentyl glycol, pentaerythritol,
myricyl alcohol, cetyl alcohol, and preference is given here to
glycerol.
[0225] It is also possible to use a mixture of various esters
and/or oils.
[0226] Component C) preferably comprises unsaturated fatty acid
fractions, corresponding to an iodine number (to DIN 53995) of from
130 to 180 mg of iodine per gram of substance, and in particular
from 120 to 200 mg of iodine per gram of substance.
[0227] The introduction of the epoxy function into the
abovementioned oils and/or esters takes place by way of reaction of
these with epoxidizing agents, e.g. peracids, such as peracetic
acid. These reactions are known to the person skilled in the art,
and there is no need for further information on this point.
[0228] The inventive molding compositions may comprise, as
component D), from 0 to 60% by weight, in particular up to 50% by
weight, of other additives and processing aids.
[0229] The inventive molding compositions may comprise, as
component D), from 0 to 5% by weight, preferably from 0.05 to 3% by
weight, and in particular from 0.1 to 2% by weight, of at least one
ester or amide of saturated or unsaturated aliphatic carboxylic
acids having from 10 to 40 carbon atoms, preferably from 16 to 22
carbon atoms, with aliphatic saturated alcohols or amines having
from 2 to 40 carbon atoms, preferably from 2 to 6 carbon atoms,
these being other than component C).
[0230] The carboxylic acids may be monobasic or dibasic. Examples
which may be mentioned are pelargonic acid, palmitic acid, lauric
acid, margaric acid, dodecanedioic acid, behenic acid, and
particularly preferably stearic acid, capric acid, and also
montanic acid (a mixture of fatty acids having from 30 to 40 carbon
atoms).
[0231] The aliphatic alcohols may be mono- to tetrahydric. Examples
of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene
glycol, propylene glycol, neopentyl glycol, pentaerythritol,
preference being given to glycerol and pentaerythritol.
[0232] The aliphatic amines may be mono-, di- or triamines.
Examples of these are stearylamine, ethylenediamine,
propylenediamine, hexamethylenediamine, di(6-aminohexyl)amine,
particular preference being given to ethylenediamine and
hexamethylenediamine. Correspondingly, preferred esters or amides
are glyceryl distearate, glyceryl tristearate, ethylenediamine
distearate, glyceryl monopalmitate, glyceryl trilaurate, glyceryl
monobehenate, and pentaerythrityl tetrastearate.
[0233] It is also possible to use mixtures of various esters or
amides, or esters with amides combined, the mixing ratio here being
as desired.
[0234] Examples of amounts of usual additives D) are up to 40% by
weight, preferably up to 30% by weight, of elastomeric polymers
(also often termed impact modifiers, elastomers, or rubbers).
[0235] These are very generally copolymers which have preferably
been built up from at least two of the following monomers:
ethylene, propylene, butadiene, isobutene, isoprene, chloroprene,
vinyl acetate, styrene, acrylonitrile and acrylates and/or
methacrylates having from 1 to 18 carbon atoms in the alcohol
component.
[0236] Polymers of this type are described, for example, in
Houben-Weyl, Methoden der organischen Chemie, Vol. 14/1
(Georg-Thieme-Verlag, Stuttgart, Germany, 1961), pages 392-406, and
in the monograph by C. B. Bucknall, "Toughened Plastics" (Applied
Science Publishers, London, UK, 1977).
[0237] Some preferred types of such elastomers are described
below.
[0238] Preferred types of such elastomers are those known as
ethylene-propylene (EPM) and ethylene-propylene-diene (EPDM)
rubbers.
[0239] EPM rubbers generally have practically no residual double
bonds, whereas EPDM rubbers may have from 1 to 20 double bonds per
100 carbon atoms.
[0240] Examples which may be mentioned of diene monomers for EPDM
rubbers are conjugated dienes, such as isoprene and butadiene,
non-conjugated dienes having from 5 to 25 carbon atoms, such as
1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,
2,5-dimethyl-1,5-hexadiene and 1,4-octadiene, cyclic dienes, such
as cyclopentadiene, cyclohexadienes, cyclooctadienes and
dicyclopentadiene, and also alkenylnorbornenes, such as
5-ethylidene-2-norbornene, 5-butylidene-2-norbornene,
2-methallyl-5-norbornene and 2-isopropenyl-5-norbornene, and
tricyclodienes, such as 3-methyltricyclo[5.2.1
.0.sup.2,6]-3,8-decadiene, and mixtures of these. Preference is
given to 1,5-hexadiene, 5-ethylidenenorbornene and
dicyclopentadiene. The diene content of the EPDM rubbers is
preferably from 0.5 to 50% by weight, in particular from 1 to 8% by
weight, based on the total weight of the rubber.
[0241] EPM and EPDM rubbers may preferably also have been grafted
with reactive carboxylic acids or with derivatives of these.
Examples of these which may be mentioned are acrylic acid,
methacrylic acid and derivatives thereof, e.g. glycidyl
(meth)acrylate, and also maleic anhydride.
[0242] Copolymers of ethylene with acrylic acid and/or methacrylic
acid and/or with the esters of these acids are another group of
preferred rubbers. The rubbers may also comprise dicarboxylic
acids, such as maleic acid and fumaric acid, or derivatives of
these acids, e.g. esters and anhydrides, and/or monomers comprising
epoxy groups. These monomers comprising dicarboxylic acid
derivatives or comprising epoxy groups are preferably incorporated
into the rubber by adding to the monomer mixture monomers
comprising dicarboxylic acid groups and/or epoxy groups and having
the general formula I, II, III, or IV
##STR00009##
where R.sup.1 to R.sup.9 are hydrogen or alkyl having from 1 to 6
carbon atoms, and m is a whole number from 0 to 20, g is a whole
number from 0 to 10 and p is a whole number from 0 to 5.
[0243] R.sup.1 to R.sup.9 are preferably hydrogen, where m is 0 or
1 and g is 1. The corresponding compounds are maleic acid, fumaric
acid, maleic anhydride, allyl glycidyl ether and vinyl glycidyl
ether.
[0244] Preferred compounds of the formulae I, II and IV are maleic
acid, maleic anhydride and (meth)acrylates comprising epoxy groups,
such as glycidyl acrylate and glycidyl methacrylate, and the esters
with tertiary alcohols, such as tert-butyl acrylate. Although the
latter have no free carboxy groups, their behavior approximates to
that of the free acids and they are therefore termed monomers with
latent carboxy groups.
[0245] The copolymers are advantageously composed of from 50 to 98%
by weight of ethylene, from 0.1 to 20% by weight of monomers
comprising epoxy groups and/or methacrylic acid and/or monomers
comprising anhydride groups, the remaining amount being
(meth)acrylates.
[0246] Particular preference is given to copolymers composed of
[0247] from 50 to 98% by weight, in particular from 55 to 95% by
weight, of ethylene, [0248] from 0.1 to 40% by weight, in
particular from 0.3 to 20% by weight, of glycidyl acrylate and/or
glycidyl methacrylate, (meth)acrylic acid and/or maleic anhydride,
and [0249] from 1 to 45% by weight, in particular from 10 to 40% by
weight, of n-butyl acrylate and/or 2-ethylhexyl acrylate.
[0250] Other preferred (meth)acrylates are the methyl, ethyl,
propyl, isobutyl and tert-butyl esters.
[0251] Besides these, comonomers which may be used are vinyl esters
and vinyl ethers.
[0252] The ethylene copolymers described above may be prepared by
processes known per se, preferably by random copolymerization at
high pressure and elevated temperature. Appropriate processes are
well known.
[0253] Other preferred elastomers are emulsion polymers whose
preparation is described, for example, by Blackley in the monograph
"Emulsion polymerization". The emulsifiers and catalysts which can
be used are known per se.
[0254] In principle it is possible to use homogeneously structured
elastomers or else those with a shell structure. The shell-type
structure is determined by the sequence of addition of the
individual monomers; the morphology of the polymers is also
affected by this sequence of addition.
[0255] Monomers which may be mentioned here, merely in a
representative capacity, for the preparation of the rubber fraction
of the elastomers are acrylates, such as n-butyl acrylate and
2-ethylhexyl acrylate, corresponding methacrylates, butadiene and
isoprene, and also mixtures of these. These monomers may be
copolymerized with other monomers, such as styrene, acrylonitrile,
vinyl ethers and with other acrylates or methacrylates, such as
methyl methacrylate, methyl acrylate, ethyl acrylate or propyl
acrylate.
[0256] The soft or rubber phase (with a glass transition
temperature of below 0.degree. C.) of the elastomers may be the
core, the outer envelope or an intermediate shell (in the case of
elastomers whose structure has more than two shells). Elastomers
having more than one shell may also have two or more shells
composed of a rubber phase.
[0257] If one or more hard components (with glass transition
temperatures above 20.degree. C.) are involved, besides the rubber
phase, in the structure of the elastomer, these are generally
prepared by polymerizing, as principal monomers, styrene,
acrylonitrile, methacrylonitrile, .alpha.-methylstyrene,
p-methylstyrene, or acrylates or methacrylates, such as methyl
acrylate, ethyl acrylate or methyl methacrylate. Besides these, it
is also possible to use relatively small proportions of other
comonomers.
[0258] It has proven advantageous in some cases to use emulsion
polymers which have reactive groups at their surfaces. Examples of
groups of this type are epoxy, carboxy, latent carboxy, amino and
amide groups, and also functional groups which may be introduced by
concomitant use of monomers of the formula
##STR00010##
where: [0259] R.sup.10 is hydrogen or C.sub.1-C.sub.4-alkyl, [0260]
R.sup.11 is hydrogen or C.sub.1-C.sub.8-alkyl or aryl, in
particular phenyl, [0261] R.sup.12 is hydrogen,
C.sub.1-C.sub.10-alkyl, C.sub.6-C.sub.12-aryl or --OR.sup.13 [0262]
R.sup.13 is C.sub.1-C.sub.8-alkyl or C.sub.6-C12-aryl, optionally
substituted by O- or N-containing groups, [0263] X is a chemical
bond or C.sub.1-C.sub.10-alkylene or C.sub.6-C.sub.12-arylene,
or
[0263] ##STR00011## [0264] Y is O-Z or NH-Z, and [0265] Z is
C.sub.1-C.sub.10-alkylene or C.sub.6-.sub.12-arylene.
[0266] The graft monomers described in EP-A 208 187 are also
suitable for introducing reactive groups at the surface.
[0267] Other examples which may be mentioned are acrylamide,
methacrylamide and substituted acrylates or methacrylates, such as
(N-tert-butylamino)ethyl methacrylate, (N,N-dimethylamino)ethyl
acrylate, (N,N-dimethylamino)methyl acrylate and
(N,N-diethylamino)ethyl acrylate.
[0268] The particles of the rubber phase may also have been
crosslinked. Examples of crosslinking monomers are 1,3-butadiene,
divinylbenzene, diallyl phthalate and dihydrodicyclopentadienyl
acrylate, and also the compounds described in EP-A 50 265.
[0269] It is also possible to use the monomers known as
graft-linking monomers, i.e. monomers having two or more
polymerizabie double bonds which react at different rates during
the polymerization. Preference is given to the use of compounds of
this type in which at least one reactive group polymerizes at about
the same rate as the other monomers, while the other reactive group
(or reactive groups), for example, polymerize(s) significantly more
slowly. The different polymerization rates give rise to a certain
proportion of double-bond unsaturation in the rubber. If another
phase is then grafted onto a rubber of this type, at least some of
the double bonds present in the rubber react with the graft
monomers to form chemical bonds, i.e. the phase grafted on has at
least some degree of chemical bonding to the graft base.
[0270] Examples of graft-linking monomers of this type are monomers
comprising allyl groups, in particular allyl esters of
ethylenically unsaturated carboxylic acids, for example allyl
acrylate, allyl methacrylate, diallyl maleate, dialiyl fumarate and
diallyl itaconate, and the corresponding monoallyl compounds of
these dicarboxylic acids. Besides these there is a wide variety of
other suitable graft-linking monomers. For further details
reference may be made here, for example, to U.S. Pat. No.
4,148,846.
[0271] The proportion of these crosslinking monomers in the
impact-modifying polymer is generally up to 5% by weight,
preferably not more than 3% by weight, based on the
impact-modifying polymer.
[0272] Some preferred emulsion polymers are listed below. Mention
may first be made here of graft polymers with a core and with at
least one outer shell, and having the following structure:
TABLE-US-00001 Type Monomers for the core Monomers for the envelope
I 1,3-butadiene, isoprene, n-butyl styrene, acrylonitrile, methyl
acrylate, ethylhexyl acrylate, methacrylate or a mixture of these
II as I, but with concomitant use of as I crosslinking agents III
as I or II n-butyl acrylate, ethyl acrylate, methyl acrylate,
1,3-butadiene, isoprene, ethylhexyl acrylate IV as I or II as I or
III, but with concomitant use of monomers having reactive groups,
as described herein V styrene, acrylonitrile, methyl first envelope
composed of methacrylate, or a mixture of monomers as described
under I these and II for the core, second envelope as described
under I or IV for the envelope
[0273] These graft polymers, in particular ABS polymers and/or ASA
polymers, are preferably used in amounts of up to 40% by weight for
the impact-modification of PBT, if appropriate in a mixture with up
to 40% by weight of polyethylene terephthalate. Blend products of
this type are obtainable with the trademark Ultradur.RTM.S
(previously Ultrablend.RTM.S from BASF AG).
[0274] Instead of graft polymers whose structure has more than one
shell, it is also possible to use homogeneous, i.e. single-shell,
elastomers composed of 1,3-butadiene, isoprene and n-butyl acrylate
or of copolymers of these. These products, too, may be prepared by
concomitant use of crosslinking monomers or of monomers having
reactive groups.
[0275] Examples of preferred emulsion polymers are n-butyl
acrylate-(meth)acrylic acid copolymers, n-butyl acrylate-glycidyl
acrylate or n-butyl acrylate-glycidyl methacrylate copolymers,
graft polymers with an inner core composed of n-butyl acrylate or
based on butadiene and with an outer envelope composed of the
abovementioned copolymers, and copolymers of ethylene with
comonomers which supply reactive groups.
[0276] The elastomers described may also be prepared by other
conventional processes, e.g. by suspension polymerization.
[0277] Preference is also given to silicone rubbers, as described
in DE-A 37 25 576, EP-A 235 690, DE-A 38 00 603 and EP-A 319
290.
[0278] It is, of course, also possible to use mixtures of the types
of rubber listed above.
[0279] Fibrous or particulate fillers D) which may be mentioned are
carbon fibers, glass fibers, glass beads, amorphous silica,
asbestos, calcium silicate, calcium metasilicate, magnesium
carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and
feldspar, used in amounts of up to 50% by weight, in particular up
to 40%.
[0280] Preferred fibrous fillers which may be mentioned are carbon
fibers, aramid fibers and potassium titanate fibers, and particular
preference is given to glass fibers in the form of E glass. These
may be used as rovings or in the commercially available forms of
chopped glass.
[0281] The fibrous fillers may have been surface-pretreated with a
silane compound to improve compatibility with the
thermoplastic.
[0282] Suitable silane compounds have the general formula:
(X--(CH.sub.2).sub.n).sub.k--Si--(O--C.sub.mH.sub.2m+1).sub.4-k
where: [0283] X is NH.sub.2--,
[0283] ##STR00012## [0284] n is a whole number from 2 to 10,
preferably 3 to 4, [0285] m is a whole number from 1 to 5,
preferably 1 to 2, and [0286] k is a whole number from 1 to 3,
preferably 1.
[0287] Preferred silane compounds are aminopropyltrimethoxysilane,
aminobutyltrimethoxysilane, aminopropyltriethoxysilane and
aminobutyltriethoxysilane, and also the corresponding silanes which
comprise a glycidyl group as substituent X.
[0288] The amounts of the silane compounds generally used for
surface-coating are from 0.05 to 5% by weight, preferably from 0.5
to 1.5% by weight and in particular from 0.8 to 1% by weight (based
on D).
[0289] Acicular mineral fillers are also suitable.
[0290] For the purposes of the invention, acicular mineral fillers
are mineral fillers with strongly developed acicular character. An
example is acicular wollastonite. The mineral preferably has an L/D
(length to diameter) ratio of from 8:1 to 35:1, preferably from 8:1
to 11:1. The mineral filler may, if appropriate, have been
pretreated with the abovementioned silane compounds, but the
pretreatment is not essential.
[0291] Other fillers which may be mentioned are kaolin, calcined
kaolin, wollastonite, talc and chalk.
[0292] As component D), the thermoplastic molding compositions of
the invention may comprise the usual processing aids, such as
stabilizers, oxidation retarders, agents to counteract
decomposition due to heat and decomposition due to ultraviolet
light, lubricants and mold-release agents, colorants, such as dyes
and pigments, nucleating agents, plasticizers, etc.
[0293] Examples which may be mentioned of oxidation retarders and
heat stabilizers are sterically hindered phenols and/or phosphites,
hydroquinones, aromatic secondary amines, such as diphenylamines,
various substituted members of these groups, and mixtures of these
in concentrations of up to 1% by weight, based on the weight of the
thermoplastic molding compositions.
[0294] UV stabilizers which may be mentioned, and are generally
used in amounts of up to 2% by weight, based on the molding
composition, are various substituted resorcinols, salicylates,
benzotriazoles, and benzophenones.
[0295] Colorants which may be added are inorganic pigments, such as
titanium dioxide, ultramarine blue, iron oxide, and carbon black,
and also organic pigments, such as phthalocyanines, quinacridones
and perylenes, and also dyes, such as nigrosine and
anthraquinones.
[0296] Nucleating agents which may be used are sodium
phenylphosphinate, alumina, silica, and preferably talc.
[0297] Other lubricants and mold-release agents are usually used in
amounts of up to 1% by weight. Preference is given to long-chain
fatty acids (e.g. stearic acid or behenic acid), salts of these
(e.g. calcium stearate or zinc stearate) or montan waxes (mixtures
of straight-chain saturated carboxylic acids having chain lengths
of from 28 to 32 carbon atoms), or calcium montanate or sodium
montanate, or low-molecular-weight polyethylene waxes or
low-molecular-weight polypropylene waxes.
[0298] Examples of plasticizers which may be mentioned are dioctyl
phthalates, dibenzyl phthalates, butyl benzyl phthalates,
hydrocarbon oils and N-(n-butyl)benzenesulfonamide.
[0299] The inventive molding compositions may also comprise from 0
to 2% by weight of fluorine-containing ethylene polymers. These are
polymers of ethylene with a fluorine content of from 55 to 76% by
weight, preferably from 70 to 76% by weight.
[0300] Examples of these are polytetrafluoroethylene (PTFE),
tetrafluoroethylene-hexafluoropropylene copolymers and
tetrafluoroethylene copolymers with relatively small proportions
(generally up to 50% by weight) of copolymerizable ethylenically
unsaturated monomers. These are described, for example, by
Schildknecht in "Vinyl and Related Polymers", Wiley-Verlag, 1952,
pages 484-494 and by Wall in "Fluoropolymers" (Wiley Interscience,
1972).
[0301] These fluorine-containing ethylene polymers have homogeneous
distribution in the molding compositions and preferably have a
particle size d.sub.50 (numeric average) in the range from 0.05 to
10 .mu.m, in particular from 0.1 to 5 .mu.m. These small particle
sizes can particularly preferably be achieved by the use of aqueous
dispersions of fluorine-containing ethylene polymers and the
incorporation of these into a polyester melt.
[0302] The inventive thermoplastic molding compositions may be
prepared by methods known per se, by mixing the starting components
in conventional mixing apparatus, such as screw extruders,
Brabender mixers or Banbury mixers, and then extruding them. The
extrudate may be cooled and comminuted. It is also possible to
premix individual components and then to add the remaining starting
materials individually and/or likewise in a mixture. The mixing
temperatures are generally from 230 to 290.degree. C.
[0303] In another preferred method of operation, components B) and
C) and, if appropriate, D) may be mixed with a prepolymer,
compounded, and pelletized. The resultant pellets are then
solid-phase-condensed, continuously or batchwise, under an inert
gas, at a temperature below the melting point of component A) until
the desired viscosity has been reached.
[0304] The inventive thermoplastic molding compositions feature
good flowability together with good mechanical properties.
[0305] In particular, the processing of the individual components
(without clumping or caking) is problem-free and possible in short
cycle times, permitting in particular an application as thin-walled
components, with very little mold deposit.
[0306] The morphology of selected compounded materials was studied
by transmission electron microscopy. Good dispersion of the
particles in the blend was seen. Particle sizes of from 20 to 500
nm were found. The typical exudation of the additives was
minimized.
[0307] These materials are suitable for the production of fibers,
foils, and moldings of any type, in particular for applications as
plugs, switches, housing parts, housing covers, headlamp bezels,
shower heads, fittings, smoothing irons, rotary switches, stove
controls, fryer lids, door handles, (rear) mirror housings, wipers
for windshields or for rear windows, sheathing for optical
conductors.
EXAMPLES
Component A:
[0308] Polybutylene terephthalate with a viscosity number VN of 130
ml/g and with a carboxy end group content of 34 meq/kg
(Ultradur.RTM. B 4500 from BASF AG) (VN measured in 0.5% strength
by weight solution of phenol/o-dichlorobenzene, 1:1 mixture at
25.degree. C.).
Preparation Specification for Polycarbonates B1
General Operating Specification:
[0309] As shown in table 1, equimolar amounts of the polyhydric
alcohol and diethyl carbonate were mixed in a three-necked flask
equipped with stirrer, reflux condenser, and internal thermometer,
and 250 ppm of catalyst (based on the amount of alcohol) were
added. The mixture was then heated with stirring to 100.degree. C.,
and in the experiment indicated by * to 140.degree. C., and stirred
for 2 h at this temperature. Evaporative cooling caused by the
monoalcohol liberated reduced the temperature of the reaction
mixture here as the reaction proceeded. The reflux condenser was
now replaced by an inclined condenser, ethanol was removed by
distillation, and the temperature of the reaction mixture was
increased slowly to 160.degree. C.
[0310] The ethanol removed by distillation was collected in a
cooled round-bottomed flask, and weighed, and the conversion was
thus determined as a percentage based on the full conversion
theoretically possible (see table 1).
[0311] The reaction products were then analyzed by gel permeation
chromatography, the eluent being dimethylacetamide and the standard
being polymethyl methacrylate (PMMA).
TABLE-US-00002 TABLE 1 Amount of ethanol distillate, based on
Molecular full weight Visc. conversion M.sub.w 23.degree. C. OH
number Alcohol Catalyst [mol %] M.sub.n [mPas] [mg KOH/g] TMP
.times. 1.2 PO K.sub.2CO.sub.3 90 2136 7200 461 1446 TMP
{circumflex over (=)} trimethylolpropane PO {circumflex over (=)}
propylene oxide
Component C: Epoxidized Soybean Oil (Epoxy Content: about 8% by
weight) (Edenol.RTM. D81 from Cognis GmbH). Component D: Glass
Fibers with Average Thickness of 10 .mu.m (Epoxysilanized Size)
Preparation of Molding Compositions
[0312] Components A) to D) were blended in a twin-screw extruder at
250 to 260.degree. C. and extruded into a waterbath. After
pelletization and drying, an injection molding machine was used to
produce test specimens and these were tested.
[0313] The pellets were injection molded to give dumbbell specimens
to ISO 527-2, and a tensile test was carried out. Impact resistance
to ISO 179-2 was also determined, as were viscosity (solvent for
PBT to DIN 53728: phenol/1,2-dichlorobenzene (1:1) ISO 1628), MVR
(ISO 1133), and also flow performance and flame retardancy to UL
94.
[0314] The inventive constitutions and the results of the
measurements are given in the tables.
TABLE-US-00003 TABLE 2 1c 2c 3 4 5 6 Component A 70 68 67.5 67.25
67 66.5 Component B 0.50 0.75 1.00 1.50 Component C 2.00 2.00 2.0
2.00 2.00 Component D 30.00 30.00 30.00 30.00 30.00 30.00 VN of
pellets 114 110 99 92 89 84 Starting material VN: specimen 106 110
97 86 83 79 110.degree. C. - aging in controlled 60 92 85 79 75 72
atmosphere, 4 days 110.degree. C. - aging in controlled 38 66 68 65
63 62 atmosphere, 8 days Mechanical properties without aging
Tensile stress at break (N/mm) 139.6 130 132.7 133.7 134.1 133.3
ISO 527-2 Tensile strain at break (%) 3.0 3.5/3.3 3.2/3.1 3 2.9 2.7
ISO 527-2 Modulus of elasticity (N/mm) 10019 9146 9298 9322 9251
9152 ISO 527-2 Impact resistance (kJ/m.sup.2) 71.7 71.8 69 68.1
62.3 53.5 ISO 179-2 MVR: 275.degree. C. - 2.16 kp 34.9 28.6 47.4
59.5 79 100 Flow spiral (260/80.degree. C. - 2 mm) 30.3 28.4 37.2
42.9 47.9 53.9 Mechanical properties, aging conditions: 4 days at
110.degree. C., 100% rel. hum. Tensile stress at break (N/mm) 84.79
121.55 119.73 118.36 115.14 112.81 ISO 527-2 Tensile strain at
break (%) 1.4 2.8 2.5 2.3 2.1 2 ISO 527-2 Modulus of elasticity
(N/mm) 9271 8702 8707 8724 8757 8682 ISO 527-2 Impact resistance
(kJ/m.sup.2) 18.4 45.7 36.4 32.7 30.2 24.7 ISO 179-2 Mechanical
properties, aging conditions: 8 days at 110.degree. C., 100% rel.
hum. Tensile stress at break (N/mm) 34.16 81.93 78.74 74.55 70.57
65.12 ISO 527-2 Tensile strain at break (%) 0.6 1.2 1.1 1.1 1 0.9
ISO 527-2 Modulus of elasticity (N/mm) 7440 8453 8591 8570 8624
8517 ISO 527-2 Impact resistance (kJ/m.sup.2) 4.8 13 13.3 12.4 10.8
11.5 ISO 179-2 c = for comparison
TABLE-US-00004 TABLE 3 1c 7c 8 9 10 11 Component A 68.5 63.5 63
62.75 62.5 62 Component B 0.50 0.75 1.00 1.50 Component C 5.00 5.00
5.0 5.00 5.00 Component D 30.00 30.00 30.00 30.00 30.00 30.00 VN of
pellets 114 118 106 99 96 94 Starting material VN: specimen 106 119
105 102 91 87 110.degree. C. - aging in controlled 60 111 98 92 87
83 atmosphere, 4 days 110.degree. C. - aging in controlled 38 104
93 90 84 78 atmosphere, 8 days Mechanical properties, without aging
Tensile stress at break (N/mm) 139.6 114.3 117.2 116.5 117.1 114.9
ISO 527-2 Tensile strain at break (%) 3.0 3.6 3.3 3.1 2.9 2.8 ISO
527-2 Modulus of elasticity (N/mm) 10019 8240 8378 9388 8463 8434
ISO 527-2 Impact resistance (kJ/m.sup.2) 71.7 65.7 67.6 65.6 60.9
58.6 ISO 179-2 MVR: 275.degree. C. - 2.16 Kp 34.9 25.9 45.2 60.7
74.8 81.4 Flow spiral (260/80.degree. C. - 2 mm) 30.3 28.9 39.9 45
49 53.6 Mechanical properties, aging conditions: 4 days at
110.degree. C., 100% rel. hum. Tensile stress at break (N/mm) 84.79
106.65 107.34 106.34 104.88 101.89 ISO 527-2 Tensile strain at
break (%) 1.4 3 2.6 2.5 2.3 2.1 ISO 527-2 Modulus of elasticity
(N/mm) 9271 7770 7953 7964 8113 8114 ISO 527-2 Impact resistance
(kJ/m.sup.2) 18.4 45.6 41.7 41.3 36.7 36.8 ISO 179-2 Mechanical
properties, aging conditions: 8 days at 110.degree. C., 100% rel.
hum. Tensile stress at break (N/mm) 34.16 97.04 98.17 96.07 94.08
89.45 ISO 527-2 Tensile strain at break (%) 0.6 2.2 2.1 1.9 1.8 1.7
ISO 527-2 Modulus of elasticity (N/mm) 7440 7729 7834 7895 8010
8038 ISO 527-2 Impact resistance (kJ/m.sup.2) 4.8 34.3 30.3 29.9
26.5 24 ISO 179-2 c = for comparison
* * * * *