U.S. patent application number 10/536869 was filed with the patent office on 2006-03-09 for mixed catalyst composition.
Invention is credited to Johannes Canisius, Andrea Kapries, Thorsten Nordhorn, Jens Roder.
Application Number | 20060052575 10/536869 |
Document ID | / |
Family ID | 32318868 |
Filed Date | 2006-03-09 |
United States Patent
Application |
20060052575 |
Kind Code |
A1 |
Roder; Jens ; et
al. |
March 9, 2006 |
Mixed catalyst composition
Abstract
The present invention relates to catalytic compositions for
esterification, transesterification and polycondensation reactions,
a process for the catalysis of said reactions employing such
catalytic compositions and polyesters or resins obtainable by this
process.
Inventors: |
Roder; Jens;
(Frankfurt/Main, DE) ; Kapries; Andrea; (Herbern,
DE) ; Nordhorn; Thorsten; (Kamen, DE) ;
Canisius; Johannes; (Bochum, DE) |
Correspondence
Address: |
Michael P Dilworth;Crompton Corporation
Beson Road
Middlebury
CT
06749
US
|
Family ID: |
32318868 |
Appl. No.: |
10/536869 |
Filed: |
November 25, 2003 |
PCT Filed: |
November 25, 2003 |
PCT NO: |
PCT/EP03/13222 |
371 Date: |
May 27, 2005 |
Current U.S.
Class: |
528/274 ;
502/150; 502/152; 502/155; 502/156 |
Current CPC
Class: |
C08G 63/87 20130101;
C08G 63/823 20130101; B01J 31/0211 20130101; C08G 63/82 20130101;
C08G 63/85 20130101; B01J 31/0212 20130101; B01J 23/14 20130101;
B01J 31/122 20130101; C07C 67/08 20130101; C07C 67/08 20130101;
C07C 69/82 20130101 |
Class at
Publication: |
528/274 ;
502/150; 502/152; 502/155; 502/156 |
International
Class: |
B01J 31/00 20060101
B01J031/00; C08G 63/87 20060101 C08G063/87 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 29, 2002 |
DE |
102 56 084.6 |
Claims
1-19. (canceled)
20. A catalytic composition useful for esterification,
transesterification and polycondensation reactions, said catalytic
composition comprising a mixture of: (A) at least one organotin
compound of the general formula (I): ##STR2## wherein R1 is
selected from the group consisting of linear, branched or cyclic
alkyl groups having 1 to 40 carbon atoms, aryl groups having 1 to
40 carbon atoms, or substituents selected from the group:
--X--R.sup.A, wherein R.sup.A is --CN, --COOH, --COO-methyl,
--COO-ethyl, --COO-n-propyl, --COO-isopropyl, --COO-n-butyl,
--COO-2-butyl, --COO-iso-butyl, --COO-tert-butyl, --COO-n-pentyl,
--COO-isopentyl, --COO-neo-pentyl, --COO-tert-pentyl, --COO-hexyl,
--COO-heptyl, --COO-n-octyl, --COO-iso-octyl,
--COO-2-ethyl-1-hexyl, --COO-2,2,4-trimethylpentyl, --COO-nonyl,
--COO-decyl, --COO-dodecyl, --COO-n-dodecyl, --COO-cyclopentyl,
--COO-cyclohexyl, --COO-cycloheptyl, --COO-methylcyclohexyl,
--COO-vinyl, --COO-1-propenyl, --COO-2-propenyl, --COO-naphtyl,
--COO-anthranyl, --COO-phenanthryl, --COO-o-tolyl, --COO-p-tolyl,
--COO-m-tolyl, --COO-tolyl, --COO-ethylphenyl, --COO-mesityl,
--COO-benzyl, --COO-phenyl, --COOC.sub.2H.sub.4OH,
--COOC.sub.3H.sub.6OH, --COOC.sub.4H.sub.8OH,
--COOCH.sub.2C(CH.sub.3).sub.2CH.sub.2OH; and --X-- is
--CH.sub.2--, --C.sub.2H.sub.4--, --C.sub.3H.sub.6--,
--C.sub.4H.sub.8--, --C.sub.5H.sub.10--, or --C.sub.6H.sub.12--; R2
is selected from the group consisting of linear, branched or cyclic
alkyl groups having 1 to 40 carbon atoms, aryl groups having 1 to
40 carbon atoms and anionic ligands with O-coordination of the
group selected from --O, --OH, linear, branched or cyclic alkyl or
arylcarboxy groups having 1 to 40 carbon atoms, linear, branched or
cyclic alkyl-, and aryl alcoholate groups having 1 to 40 carbon
atoms; and R3 and R4 are each independently selected from the group
consisting of anionic ligands with O-coordination of the group
selected from --O, --OH, linear, branched or cyclic alkyl groups or
arylcarboxy groups having 1 to 40 carbon atoms, linear, branched or
cyclic alkyl-, and aryl alcoholate groups having 1 to 40 carbon
atoms and anions of a mineral acid selected from the group of
sulphate, sulphite, phosphate, halogen- or pseudohalogen anion; and
(B) at least one compound according to one of the formulae (II),
(III) and/or (IV), X.sub.m(R').sub.n (formula II)
O.dbd.X.sub.m(R').sub.o (formula III)
(O.dbd.).sub.rX.sub.mO.sub.p(R').sub.q (formula IV) wherein X is a
heteroatom selected from the group consisting of N, Si, Cl, Br, I
or S, m is an integer from 1 to 5, n is an integer from 1 to 5, o
is an integer from 1 to 5, p is an integer from 0 to 5, q is an
integer from 0 to 5, r is an integer from 0 to 3, R' in formula
(II) denotes n different or identical groups, each being
independent from each other and selected from the group of linear,
branched or cyclic alkyl groups having 1 to 40 carbon atoms, aryl
groups having 1 to 40 carbon atoms, anionic ligands with
O-coordination selected from the group of --O, --OH, linear,
branched or cyclic alkyl-, and aryl alcoholate groups having 1 to
40 carbon atoms, H, Cl, Br, NH.sub.4.sup.+ or a metal ion, R' in
formula (III) denotes o different or identical groups, each being
independent from each other and selected from the group of linear,
branched or cyclic alkyl groups having 1 to 40 carbon atoms, aryl
groups having 1 to 40 carbon atoms, anionic ligands with
O-coordination selected from the group of --O, --OH, linear,
branched or cyclic alkyl-, and aryl alcoholate groups having 1 to
40 carbon atoms, H, Cl, Br, NH.sub.4.sup.+ or a metal ion, R' in
formula (IV) denotes q different or identical groups, each being
independent from each other and selected from the group of linear,
branched or cyclic alkyl groups having 1 to 40 carbon atoms, aryl
groups having 1 to 40 carbon atoms, anionic ligands with
O-coordination selected from the group of --O, --OH, linear,
branched or cyclic alkyl-, and arylalcoholate groups having 1 to 40
carbon atoms, H, Cl, Br, NH.sub.4.sup.+ or a metal ion, or X is P,
then m is an integer from 1 to 5, n is an integer from 1 to 5, o is
an integer from 1 to 5, p is an integer from 0 to 5 q is an integer
from 0 to 5, r is an integer from 0 to 3, R' in formula (II)
denotes n different or identical groups, each being independent
from each other and selected from the group of linear, branched or
cyclic alkyl groups having 1 to 40 carbon atoms, aryl groups having
1 to 40 carbon atoms, anionic ligands with O-coordination selected
from the group of --O, --OH, linear, branched or cyclic alkyl-, and
aryl alcoholate groups having 1 to 40 carbon atoms, H, Cl, Br,
NH.sub.4.sup.+ or a metal ion, R' in formula (III) denotes o
different or identical groups, each being independent from each
other and selected from the group of linear, branched or cyclic
alkyl groups having 1 to 40 carbon atoms, aryl groups having 1 to
40 carbon atoms, anionic ligands with O-coordination selected from
the group of --O, --OH, linear, branched or cyclic alkyl-, and aryl
alcoholate groups having 1 to 40 carbon atoms, H, Cl, Br,
NH.sub.4.sup.+ or a metal ion, and R' in formula (IV) denotes q
different or identical groups, each being independent from each
other selected from the group of linear, branched or cyclic alkyl
groups having 1 to 40 carbon atoms, aryl groups having 1 to 40
carbon atoms, anionic ligands with O-coordination selected from the
group of --O, linear, branched or cyclic alkyl-, and aryl
alcoholate groups having 1 to 40 carbon atoms, H, Cl, Br,
NH.sub.4.sup.+ or a metal ion.
21. The catalytic composition according to claim 20, wherein the
metal ion is selected from the group consisting of NH.sub.4, Li,
Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, B, Al, Sc and Y.
22. The catalytic composition according to claim 20, wherein (B) is
a phosphite, a phosphine, a phosphonic acid ester, a pyrophosphate,
an alkaline halogenide, an earth alkaline halogenide or aluminum
halogenide.
23. The catalytic composition according to claim 20, comprising a
molar ratio of (A) to (B) of 1:0.001 to 1:200, in particular 1:0.01
to 1:20, respectively.
24. The catalytic composition according to claim 20, further
comprises a suspension agent or solvent.
25. A process for the continuous or batchwise catalysis of
esterification, transesterification, polyesterification,
polytransesterification reactions of an alcohol and an acid or acid
derivative, such as an ester, anhydride or halogenide, said process
employing the catalytic composition as defined in claim 20.
26. The process according to claim 25, employing an amount of (A)
in the range of 0.1 to 1% by weight, in particular 10 to 200 ppm,
with respect to the acid or ester to be reacted.
27. The process according to claim 26, employing a concentration of
(B) in the range of 0.0001 ppm to 1% by weight, in particular 10 to
200 ppm, with respect to the acid or ester to be reacted.
28. The process according to claim 25, employing a concentration of
(B) in the range of 0.0001 ppm to 1% by weight, in particular 10 to
200 ppm, with respect to the acid or ester to be reacted.
29. The process according to claim 25, comprising reacting a
dicarboxylic acid or a dicarboxylic acid derivative with a divalent
alcohol in the polyesterification reaction.
30. The process according to claim 25, employing derivatives of
mono-, di or polycarboxylic acids selected from esters or
halogenides.
31. The process according to claim 25, comprising reacting
hydroxycarboxylic acids or derivatives of hydroxycarboxylic acids
in the esterification, transesterification, polyesterification or
polytransesterification reaction.
32. The process according to claim 31, employing derivatives of
hydroxycarboxylic acids selected from esters or ethers.
33. The process according to claim 25, employing a solvent or
suspending agent added to (A) and (B).
34. The process according to claim 33, employing an alkane mono-,
di- or polyvalent alcohol as the solvent or suspending agent.
35. The process according to claims 33, employing the same solvent
and/or suspending agent during manufacturing of the catalytic
composition and said esterification, transesterification,
polyesterification or polytransesterification reaction.
36. The process according to claim 35, employing a solvent selected
from the group consisting of mono-, di- or polyvalent alcohols
reacted in said esterification, transesterification,
polyesterificatin or polytransesterification reaction.
37. The process according to claim 33, employing a different
solvent and/or suspending agent during manufacturing the catalytic
composition and said esterification, transesterification,
polyesterification or polytransesterification reaction.
38. A composition comprising polyester for bottles, films, foils,
yarn and/or molded padding, or resin for powder coatings or
technical synthetic materials, obtained by the process according to
claim 25.
39. The polyester or resin composition according to claim 38,
wherein said polyester is selected from the group consisting of
polyethylene terephthalate,
poly-2,2-dimethylpropyl-1,3-terephthalate, polypropylene
terephthalate, polydiethyleneglycol terephthalate, polybutylene
terephthalate, polynaphthalene terephthalate, polyethylene
naphthalate, and mixtures thereof.
Description
[0001] The present invention relates to catalytic compositions for
esterification, transesterification and polycondensation reactions,
a process for the catalysis of said reactions employing such
catalytic compositions and polyesters or resins obtainable by this
process.
[0002] Catalytic systems containing organotin compounds are widely
known. JP-A 06-248060, JP-A 03-284414 and JP-A 03-218511 describe
catalyst systems based on organo tin compounds and trivalent and
pentavalent heteroatom compounds especially phosphorous ligands,
used in the ring opening polymerization of lactides. These systems
are used to optimize the mechanical and thermal resistance of the
polymer.
[0003] The application of such catalytic compositions for carrying
out or accelerating other reactions has not been reported so
far.
[0004] In contrast, DE-A-101 21 542 reports further that e.g.
stabilizers containing heteroatoms are used for quenching the
catalyst within the esterification, transesterification or
pre-condensation step as these compounds form inactive products
together with the catalyst.
[0005] Furthermore, special processes are known in which defined
catalyst and stabilizer concentrations and defined locations for
their addition are used. Herein the stabilizer is added after the
catalyst. According to DE-A-19 50 997 it is common to deactivate
the transesterification catalyst with a suited amount of a
trivalent or pentavalent heteroatom containing compound by
coordination or covalent bonding. This is done to avoid a
detrimental influence of the transesterification catalyst within
the polycondensation reaction. The polycondensation catalyst is
added after this deactivation, a further polycondensation
stabilizer might be added later.
[0006] Furthermore is known that during the production of
polyesters for some applications for example wrappings and
technical yarns, a crystallization and polycondensation in the
solid state is carried out (U.S. Pat. No. 4,064,112, U.S. Pat. No.
4,263,425, U.S. Pat. No. 5,362,844). In other applications, fibers
or filaments are spun directly and direct preforms are produced in
a process wherein an intermediate transfer into the solid state and
a repeated remelting is not applied.
[0007] Conventional polyester compositions are connected with a
series of disadvantages (general summary in: Handbook of polyester
thermoplastics, 1st edition, Wiley-VCH, Weinheim, 2002). Among
these disadvantages are in particular: [0008] Necessity of high
temperatures for the synthesis [0009] High catalyst concentration
(100-500 ppm [as metal]) [0010] Degradation processes under
processing and polycondensation conditions; for example formation
of vinyl esters and due to the formation of acetic aldehyde in
polyethylene terephthalate (PET), formation of acrolein in
polypropylene terephthalate (PPT) and tetrahydrofuran formation in
polybutylene terephthalate (PBT). [0011] Limited use of the
catalyst systems, dependent on the technology of the process and
the chemical structure of the substrate; classic titanium based
catalysts cannot be added for example during the esterification-
and/or pre/condensation step, as these are readily hydrolyzed to
inactivate titanium oxides. [0012] Application of the catalyst
system only in selected process stages for example only during the
esterifications- or only during the transesterification- or only
during the polycondensation stage. [0013] Optical turbidity of the
produced polyester for example by deposits of elementary metal
impurities as this can occur by the use of antimony based catalyst
systems. [0014] Discoloration of the polyester by the catalyst
itself, for example titanium based catalyst systems cause a yellow
coloring of the polymer or formation of chromophor by-products,
respectively. [0015] Problematic metering and addition of catalysts
and catalyst formulations.
[0016] Object of the present invention is to provide a catalytic
composition, suitable for catalyzing esterification,
transesterification and polycondensation reactions, an improved
process of esterification, transesterification and polycondensation
reactions and the production of improved polyesters for bottles,
films, foils, yarn, molded padding, resins for powder coatings and
technical synthetic materials, which avoid the disadvantages of the
prior art.
[0017] The problem is solved according to the invention by a
catalytic composition according to claim 1, a process according to
claim 6 and polyesters or resins according to claims 18 and 19.
[0018] The catalytic composition for esterification,
transesterification and polycondensation reactions according to the
invention contains a mixture of at least one organotin compound
(compound I) of the general formula (I): ##STR1## [0019] wherein
[0020] R1 is selected from the group of linear, branched or cyclic
alkyl groups having 1 to 40 carbon atoms, aryl groups having 1 to
40 carbon atoms, or substituents selected from the group:
--X-R.sup.A, wherein R.sup.A is --CN, --COOH, --COO-methyl,
--COO-ethyl, --COO-n-propyl, --COO-isopropyl, --COO-n-butyl,
--COO-2-butyl, --COO-iso-butyl, --COO-tert-butyl, COO-n-pentyl,
--COO-isopentyl, --COO-neo-pentyl, --COO-tert-pentyl, COO-hexyl,
--COO-heptyl, --COO-n-octyl, --COO-iso-octyl,
--COO-2-ethyl-1-hexyl, --COO-2,2,4-trimethylpentyl, --COO-nonyl,
--COO-decyl, --COO-dodecyl, --COO-n-dodecyl, --COO-cyclopentyl,
--COO-cyclohexyl, --COO-cycloheptyl, --COO-methylcyclohexyl,
--COO-vinyl, --COO-1-propenyl, --COO-2-propenyl, --COO-naphtyl,
--COO-anthranyl, --COO-phenanthryl, --COO-o-tolyl, --COO-p-tolyl,
--COO-m-tolyl, --COO-tolyl, --COO-ethylphenyl, --COO-mesityl,
--COO-benzyl, --COO-phenyl, --COOC.sub.2H.sub.4OH,
--COOC.sub.3H.sub.6OH, --COOC.sub.4H.sub.8OH,
--COOCH.sub.2C(CH.sub.3).sub.2CH.sub.2OH; and --X-- is
--CH.sub.2--, --C.sub.2H.sub.4--,
--C.sub.3H.sub.6--C.sub.4H.sub.8--, --C.sub.5H.sub.10--, or
--C.sub.6H.sub.12--; [0021] R2 is selected from the groups of
linear, branched or cyclic alkyl groups having 1 to 40 carbon
atoms, aryl groups having 1 to 40 carbon atoms and anionic ligands
with O-coordination of the group selected from -O, --OH, linear,
branched or cyclic alkyl or arylcarboxy groups having 1 to 40
carbon atoms, linear, branched or cyclic alkyl-, and aryl
alcoholate groups having 1 to 40 carbon atoms; [0022] R3 and R4
independently each are selected from the groups of anionic ligands
with O-coordination of the group selected from -O, --OH, linear,
branched or cyclic alkyl groups or arylcarboxy groups having 1 to
40 carbon atoms, linear, branched or cyclic alkyl-, and aryl
alcoholate groups having 1 to 40 carbon atoms and anions of a
mineral acid selected from the group of sulphate, sulphite,
phosphate, halogen- or pseudohalogen anion and at least one
compound (compound II) according to one of the formulae (II), (III)
and/or (IV), X.sub.m(R').sub.n (Formula II) O.dbd.X.sub.m(R').sub.o
(Formula III) (O.dbd.).sub.rX.sub.mO.sub.p(R').sub.q (Formula IV)
wherein X is a heteroatom selected from the group consisting of N,
P, Si, Cl, Br, I or S, [0023] m is an integer from 1 to 5, [0024] n
is an integer from 1 to 5, [0025] o is an integer from 1 to 5,
[0026] p is an integer from 0 to 5, [0027] q is an integer from 0
to 5, [0028] r is an integer from 0 to 3, wherein [0029] R' in
formula (II) denotes n different or identical groups, each being
independent from each other selected from the group of linear,
branched or cyclic alkyl groups having 1 to 40 carbon atoms, aryl
groups having 1 to 40 carbon atoms, anionic ligands with
O-coordination selected from the group of -O, --OH, linear,
branched or cyclic alkyl-, and aryl alcoholate groups having 1 to
40 carbon atoms, H, Cl, Br, NH.sub.4.sup.+ or a metal ion, [0030]
R' in formula (III) denotes o different or identical groups, each
being independent from each other selected from the group of
linear, branched or cyclic alkyl groups having 1 to 40 carbon
atoms, aryl groups having 1 to 40, anionic ligands with
O-coordination selected from the group of -O, --OH, linear,
branched or cyclic alkyl-, and arylalcoholate groups having 1 to 40
carbon atoms, H, Cl, Br, NH.sub.4.sup.+ or a metal ion, R' in
formula (IV) denotes q different or identical groups, each being
independent from each other selected from the group of linear,
branched or cyclic alkyl groups having 1 to 40 carbon atoms, aryl
groups having 1 to 40, anionic ligands with O-coordination selected
from the group of -O, --OH, linear, branched or cyclic alkyl-, and
arylalcoholate groups having 1 to 40 carbon atoms, H, Cl, Br,
NH.sub.4.sup.+ or a metal ion.
[0031] Said catalytic compositions proved highly effective in the
catalysis of esterification, transesterification, polycondensation,
polyesterification and polytransesterification reactions.
[0032] It has to be pointed out that according to the invention
compound I and compound II form a physical mixture and do not
chemically react with each other. That means compound I and
compound II are neither connected by a complex nor a covalent bond.
For example, in the case that compound II is a phosphorous compound
this is confirmed by the .sup.31P NMR data of the physical mixture
of compound I and compound II.
[0033] Preferred metal ions according to the invention include
NH.sub.4, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Zn, B, Al, Sc, Y.
[0034] Preferred examples for compound I are defined by R1=methyl,
ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl,
tert-butyl, n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl,
heptyl, n-octyl, iso-octyl, 2-ethyl-1-hexyl, 2,2,4-trimethylpentyl,
nonyl, decyl, dodecyl, n-dodecyl, cyclopentyl, cyclohexyl,
cycloheptyl, methylcyclohexyl, vinyl, 1-propenyl, 2-propenyl,
naphthyl, anthranyl, phenanthryl, o-tolyl, p-tolyl, m-tolyl, xylyl,
ethylphenyl, mesityl, phenyl, benzyl, or R1 a substituent from the
group: --X-R.sup.A with R.sup.A=--CN, --COOH, --COO-methyl,
--COO-ethyl, --COO-n-propyl, --COO-iso-propyl, --COO-n-butyl,
--COO-2-butyl, --COO-iso-butyl, --COO-tert-butyl, --COO-n-pentyl,
--COO-isopentyl, --COO-neo-pentyl, --COO-tert-pentyl, --COO-hexyl,
--COO-heptyl, --COO-n-octyl, --COO-iso-Octyl,
--COO-2-Ethyl-1-hexyl, --COO-2,2,4-trimethylpentyl, --COO-nonyl,
--COO-decyl, --COO-dodecyl, --COO-n-dodecyl, --COO-cyclopentyl,
--COO-cyclohexyl, --COO-cycloheptyl, --COO-methylcyclohexyl,
--COO-Vinyl, --COO-1-propenyl, --COO-2-propenyl, --COO-naphtyl,
--COO-ahthranyl, --COO-phenanthryl, --COO-o-tolyl, --COO-p-tolyl,
--COO-m-tolyl, --COO-xylyl, --COO-ethylphenyl, --COO-mesityl,
--COO-benzyl, --COO-phenyl, --COOC.sub.2H.sub.4OH,
--COOC.sub.3H.sub.6OH, --COOC.sub.4H.sub.8OH,
--COOCH.sub.2C(CH.sub.3).sub.2CH.sub.2OH; with --X--: --CH.sub.2--,
--C.sub.2H.sub.4--, --C.sub.3H.sub.6--, --C.sub.4H.sub.8--,
--C.sub.5H.sub.10--, --C.sub.6H.sub.12--.
[0035] Especially preferred substituents according to the invention
are: methyl, n-butyl, n-octyl und n-dodecyl.
[0036] According to the invention --X-- is preferably
--C.sub.2H.sub.4--, and preferred moieties R.sup.A are --CN,
--COOH, --COO-methyl, --COO-ethyl.
[0037] Preferred examples for R2 are according to the invention:
[0038] a) methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl,
iso-butyl, tert-butyl, n-pentyl, iso-pentyl, neo-pentyl,
tert-pentyl, hexyl, heptyl, n-octyl, iso-octyl, 2-ethyl-1-hexyl,
2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl,
cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl,
1-propenyl, 2-propenyl, naphthyl, anthranyl, phenanthryl, o-tolyl,
p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, benzyl.
Favored substituents for the invention are: Methyl, butyl, octyl
and dodecyl, or [0039] b) 0, OH, methanolate, ethanolate,
n-propanolate, iso-propanolate, n-butanolate, 2-butanolate,
iso-butanolate, tert-butanolate, n-pentanolate, iso-pentanolate,
neo-pentanolate, tert-pentanolate, 2-methyl-1-butanolate,
hexanolate, heptanolate, n-octanolate, iso-octanolate,
2,2,4-trimethylpentanolate, nonanolate, decanolate, dodecanolate,
n-dodecanolate, cyclopentanolate, cyclohexanolate,
cycloheptanolate, methylcyclohexanolate, glycolate, glycerate,
pinacolate neopentylglycolate, vinylalcoholate,
propargylalcoholate, 2-ethyl-1-hexanolate, formiate, acetate,
propionate, butyrate, valeriate, caprate, caprylate, caprinate,
laurate, laureate, 2-ethyl-1-hexanoate, neodecanoate, palmitate,
stearate, benzoate, terephthalate, phthalate, isoterephthalate,
acrylate, methacrylate, crotonate, isocrotonate, vinylacetate,
oleate, sorbate, linolate, linolenate, trifluoracetate,
p-toluolsulfonate, oxalate, malonate, succinate, glutarate,
adipate, fumarate, maleinate, carboxylates of the following
monoesters: methylmaleicacid monoester, ethylmaleicacid monoester
butylmaleicacid monoester, n-propylmaleicacid monoester,
iso-propyl-maleicacid monoester, n-butylmaleicacid monoester,
2-butylmaleicacid monoester, iso-butylmaleicacid monoester,
tert-butylmaleicacid monoester, n-pentylmaleicacid monoester,
isopentylmaleicacid monoester, neo-pentylmaleicacid monoester,
tert-pentylmaleicacid monoester, 2-methyl-1-butylmaleicacid
monoester, hexylmaleicacid monoester, heptylmaleicacid monoester,
n-octylmaleicacid monoester, iso-octylmaleicacid monoester,
2,2,4-trimethylpentylmaleicacid monoester, nonylmaleicacid
monoester, decylmaleicacid monoester, dodecylmaleicacid monoester,
n-dodecylmaleicacid monoester, cyclopentylmaleicacid monoester,
cyclohexylmaleicacid monoester, cycloheptylmaleicacid monoester,
methylcyclohexylmaleicacid monoester, glycolmaleicacid monoester,
glycerolmaleicacid monoester, pinakolmaleicacid monoester,
neopentylglycolmaleicacid monoester, vinylmaleicacid monoester,
propargylmaleicacid monoester and 2-ethyl-1-hexylmaleicacid
monoester, citrate, lactate, tartrate, naphtenate,
naphthalen-2,6-dicarboxalate, naphthalene-1,6-dicarboxalate, F, Cl,
ClO, ClO.sub.2, ClO.sub.3, ClO.sub.4, Br, J, CN, SCN, OCN,
sulphate, hydrogensulphate, sulphite, hydrogensulphite, sulphide,
phosphate, hydrogenphosphate, dihydrogenphosphate,
bis(2-ethyl-1-hexyl)phosphate, butylphosphate, dibutylphosphate,
3-phosphonopropionate, phenylphosphonacid, benzolphosphonigacid,
p-aminophosphonacid, n-octylphosphonacid favored substituents are:
O, OH, laureate, 2-ethyl-1-hexanoate, neodecanoate, oxalate,
2-ethyl-1-hexylmaleicacid monoester and acetate.
[0040] Preferred examples for R3 and R4 are according to the
invention: 0, OH, methanolate, ethanolate, n-propanolate,
iso-propanolate, n-butanolate, 2-butanolate, iso-butanolate,
tert-butanolate, n-pentanolate, iso-pentanolate, neo-pentanolate,
tert-pentanolate, 2-methyl-1-butanolate, hexanolate, heptanolate,
n-octanolate, iso-octanolate, 2,2,4-trimethylpentanolate,
nonanolate, decanolate, dodecanolate, n-dodecanolate,
cyclopentanolate, cyclohexanolate, cycloheptanolate,
methylcyclohexanolate, glycolate, glycerate, pinacolate
neopentylglycolate, vinylalcoholate, propargylalcoholate,
2-ethyl-1-hexanolate, formiate, acetate, propionate, butyrate,
valeriate, caprate, caprylate, caprinate, laureate,
2-ethyl-1-hexanoate, neodecanoate, palmitate, stearate, benzoate,
terephthalate, phthalate, isoterephthalate, acrylate, methacrylate,
crotonate, isocrotonate, vinylacetate, oleate, sorbate, linolate,
linolenate, trifluoracetate, p-toluolsulfonate, oxalate, malonate,
succinate, glutarate, adipate, fumarate, maleinate,
methylmaleicacid monoester, ethylmaleicacid monoester,
butylmaleicacid monoester, n-propylmaleicacid monoester,
iso-propylmaleicacid monoester, n-butylmaleicacid monoester,
2-butylmaleicacid monoester, iso-butylmaleicacid monoester,
tert-butylmaleicacid monoester, n-pentylmaleicacid monoester,
isopentylmaleicacid monoester, neo-pentylmaleicacid monoester,
tert-pentylmaleicacid monoester, 2-methyl-1-butylmaleicacid
monoester, hexylmaleicacid monoester, heptylmaleicacid monoester,
n-octylmaleicacid monoester, iso-octylmaleicacid monoester,
2,2,4-trimethylpentylmaleicacid monoester, nonylmaleicacid
monoester, decylmaleicacid monoester, dodecylmaleicacid monoester,
n-dodecylmaleicacid monoester, cyclopentylmaleicacid monoester,
cyclohexylmaleicacid monoester, cycloheptylmaleicacid monoester,
methylcyclohexylmaleicacid monoester, glycolmaleicacid monoester,
glycerolmaleic acid monoester, pinacolmaleicacid monoester,
neopentylglycolmaleicacid monoester, vinylmaleicacid monoester,
propargylmaleicacid monoester and 2-ethyl-1-hexylmaleicacid
monoester, citrate, lactate, tartrate, naphtenate,
naphthalene-2,6-dicarboxalate, naphthalene-1,6-dicarboxalate, F,
Cl, ClO, ClO.sub.2, ClO.sub.3, ClO.sub.4, Br, J, CN, SCN, OCN,
sulphate, hydrogensulphate, sulphite, hydrogensulphite, sulphide,
phosphate, hydrogenphosphate, dihydrogenphosphate,
bis(2-ethyl-1-hexyl)phosphate, butylphosphate, dibutylphosphate,
3-phosphonopropionate, phenylphosphonacid, benzoenephosphonigacid,
p-aminophosphonacid, n-octylphosphonacid. Most preferred
substituents are: O, OH, Cl, laureate, 2-ethyl-1-hexanoate,
neodecanoate, oxalate, 2-ethyl-1-hexylmaleicacid monoester and
acetate.
[0041] Preferred examples for compound II of the invention are
phosphites, phosphines, phosphonic acid esters, pyrophosphates,
alkaline halogenides, earth alkaline halogenides, aluminum
halogenides.
[0042] According to the invention combinations with the following
examples of compound II are particularly preferred: Formula II
(X.dbd.P): trioctyl-, triisooctyl-, trilauryl, tridecyl-,
tridodecyl-, triisododecyl-, tritridecyl-, tripentadecyl-,
trioleyl, tristearyl-, triphenyl-, trikresyl-, tris-nonylphenol,
tris-2,4-t-butyl-phenyl- or tricyclohexylphosphite.
[0043] Further preferred phosphites of several aryl-dialkyl or
alkyl-diarylphosphite may be advantageously applied, such as
phenyldi-octyl-, phenyldidecyl-, phenyldidodecyl-,
phenylditridecyl-, phenylditetradecyl-, phenyldipentadecyl-,
octyldiphenyl-, decycidiphenyl-, undecyldiphenyl-,
dodecyidiphenyl-, tridecyidiphenyl-, tetradecyldiphenyl-,
pentadecyldi-phenyl-, oleyldiphenyl-, stearyldiphenyl-und
dodecyl-bis-2,4-di-t-butylphenylphosphite,
tris(2,4-di-tert-butylphenyl)phosphite,
diphenyl-isodecylphosphite.
[0044] Also phosphites of several di- or polyols are very well
suited and therefore preferred, e.g.
phenylneopentylenglycolphosphite,
heptakis-(dipropyleneglycol)triphosphite,
2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propandiolphosphite,
bis(2,4-tri-tert-butylphenyl)penta-erythritoldiphosphite,
tetraphenyldipropylenglykoldiphosphite,
polydi-propyleneglykolphenylphosphite,
tetramethylolcyclohexanol-decyidi-phosphite,
tetramethylolcyclohexanol-butoxyethoxy-ethyldiphosphite,
tetramethylolcyclohexanol-nonylphenyldiphosphite,
bis-nonylphenyl-di-trimethylolpropanediphosphite,
bis-2-butoxyethyl-di-trimethylol-propan-ediphosphite,
trishydroxyethylisocyanurat-hexadecyltriphosphite,
tris(dipropyleneglycol)phosphite,
poly-4,4'-isopropylidendiphenol-c12-15-alcoholphosphite,
diisodecylpentaerythritoldiphosphite,
didecylpenta-erythritdiphosphite,
distearylpentaerythritdiphosphite, also mixtures of these
phosphites and aryl/alkylphosphite-mixtures of the statistic
composition
(H.sub.19C.sub.9-C.sub.6H.sub.4)O.sub.1,5P(OC.sub.12,13H.sub.25,27).sub.1-
,5 or
[C.sub.8H.sub.17--C.sub.6H.sub.4--O-].sub.2P[i-C.sub.8H.sub.17O]
(H.sub.19C.sub.9-C.sub.6H.sub.4)O.sub.1,5P(OC.sub.9,11H.sub.19,23).sub.1,-
5 are suitable as well as phosphines with R1', R2', R3'=methyl,
ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl,
tert-butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, hexyl,
heptyl, n-octyl, iso-octyl, 2,2,4-trimethylpentyl, nonyl, decyl,
dodecyl, n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl,
methylcyclohexyl, o-tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl,
mesityl, phenyl, benzyl and also DIOP, Chiraphos and Norphos.
[0045] According to the invention especially favored are heteroatom
compounds II including heteroatoms such as according to formula II
wherein R1', R2' and R3' are each independently selected from
C.sub.6H.sub.5, OC.sub.6H.sub.5 and OC.sub.4H.sub.9.
[0046] Moreover, according to the invention mixtures of compound I
with a compound II according to formula III are particularly
preferred, such as e.g. (X.dbd.P): R1', R2', R3'=Methyl, ethyl,
n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl,
n-pentyl, iso-pentyl, neo-pentyl, tert-pentyl, hexyl, heptyl,
n-octyl, iso-octyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl,
n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl,
vinyl, 1-propenyl, 2-propenyl naphthyl, anthryl, phenanthryl,
o-tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl,
benzyl, methanolate, ethanolate, n-propanolate, iso-propanolate,
n-butanolate, 2-butanolate, iso-butanolate, tert-butanolate,
n-pentanolate, isopentanolate, neo-pentanolate, tert-pentanolate,
2-methyl-1-butanolate, hexanolate, heptanolate, n-octanolate,
iso-octanolate, 2,2,4-trimethylpentanolate, nonanolate, decanolate,
dodecanolate, n-dodecanolate, cyclopentanolate, cyclohexanolate,
cycloheptanolate, methylcyclohexanolate, glycolate, glycerate,
pinacolate, neopentylglycolate, vinylalcoholate,
propargylalcoholate, 2-ethyl-1-hexanolate, ethyleneglycol,
diethyleneglycol, triethyleneglycol und benzylalcoholate and for
X=2: tetramethylpyrophosphate, tetra ethylpyrophosphate,
tetrakis-n-propylpyrophosphate, tetrakis-iso-propyl pyrophosphate,
tetrakis-n-butylpyrophosphate, tetrakis-2-butylpyro-phosphate,
tetrakis-iso-butylpyrophosphate, tetrakis-tert-butylpyro-phosphate,
tetrakis-n-pentylpyrophosphate, tetrakis-iso-pentylpyro-phosphate,
tetrakis-neo-pentylpyrophosphate,
tetrakis-tert-pentylpyro-phosphate, tetrahexylpyrophosphate,
tetraheptylpyrophosphate, tetrakis-n-octylpyrophosphate,
tetrakis-iso-octylpyrophosphate,
tetrakis-2-ethyl-1-hexylpyrophosphate,
tetrakis-2,2,4-trimethylpentyl-pyrophosphate,
tetranonylpyrophosphate, tetradecylpyrophosphate,
tetradodecylpyrophosphate, tetrakis-n-dodecylpyrophosphate,
tetra-cyclopentylpyrophosphate, tetracyclohexylpyrophosphate,
tetracyclo-heptylpyrophosphate,
tetrakis-methylcyclohexylpyrophosphate,
tetra-naphthylpyrophosphate, tetraanthrylpyrophosphate,
tetraphenanthryl-pyrophosphate, tetrakis-o-tolylpyrophosphate,
tetrakis-p-tolylpyro-phosphate, tetrakis-m-tolylpyrophosphate,
tetraxylylpyrophosphate, tetrakis-ethylphenylpyrophosphate,
tetramesitylpyrophosphate, tetra-phenylpyrophosphate,
tetrabenzylpyrophosphate or R1', R2'=Methyl, ethyl, n-propyl,
iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl,
isopentyl, neo-pentyl, tert-pentyl, hexyl, heptyl, n-octyl,
iso-octyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl,
cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, vinyl,
1-propenyl, 2-propenyl naphtyl, anthryl, phenanthryl, o-tolyl,
p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, benzyl,
methanolate, ethanolate, n-propanolate, iso-propanolate,
n-butanolate, 2-butanolate, iso-butanolate, tert-butanolate,
n-pentanolate, isopentanolate, neo-pentanolate, tert-pentanolate,
2-methyl-1-butanolate, hexanolate, heptanolate, n-octanolate,
iso-octanolate, 2,2,4-trimethylpentanolate, nonanolate, decanolate,
dodecanolate, n-dodecanolate, cyclo-pentanolate, cyclohexanolate,
cycloheptanolate, methylcyclohexanolate, glycolate, glycerate,
pinacolate neopentylglycolate, vinylalcoholate,
propargylalcoholate, 2-ethyl-1-hexanolate, ethylenglycol,
dieethylene-glycol, triethylenglycol and benzylalcoholate, R3'=H
such as e.g. diphenylphosphite. Triphenylphosphinoxide,
triethylphosphate, tributyl-phosphate, triphenylphosphate,
tris(triethylenglycol)phosphate and diphenylphosphite are
especially preferred.
[0047] Further, according to the invention mixtures of compound I
with one or more of the following examples of compound II are
particularly preferred (Formula II, X.dbd.N): Trioctyl-,
trilsooctyl-, trilauryl, tridecyl-, tridodecyl-, triisododecyl-,
tritridecyl-, tripentadecyl-, trioleyl, tristearyl-, triphenyl-,
trikresyl-, tris-nonylphenol, tris-2,4-t-butyl-phenyl-,
tricyclohexylamine, also amines with a composition R1', R2',
R3'=independent, the same or different: methyl, ethyl, n-propyl,
iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl,
isopentyl, neo-pentyl, tert-pentyl, hexyl, heptyl, n-octyl,
iso-octyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl,
cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, o-tolyl,
p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, benzyl are
suitable, as well as R1', R2', R3', R4'=H, R5'=Cl, or R1', R2',
R3', R4' H, R5'=Br.
[0048] Mixtures of compound I with one or more of the following
examples of compound II of formula II are according to the
invention preferred (X.dbd.Si): R1', R2', R3'=independent, the same
or different: methyl, ethyl, n-propyl, iso-propyl, n-butyl,
2-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl,
tert-pentyl, hexyl, heptyl, n-octyl, iso-octyl,
2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl,
cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, O-tolyl,
p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, benzyl,
R4'=O, OH, methanolate, ethanolate, n-propanolate, iso-propanolate,
n-butanolate, 2-butanolate, iso-butanolate, tert-butanolate,
n-pentanolate, iso-pentanolate, neo-pentanolate, tert-pentanolate,
2-methyl-1-butanolate, hexanolate, heptanolate, n-octanolate,
iso-octanolate, 2,2,4-trimethylpentanolate, nonanolate, decanolate,
dodecanolate, n-dodecanolate, cyclo-pentanolate, cyclohexanolate,
cycloheptanolate, methylcyclohexanolate, glycolate, glycerate,
pinacolate neopentylglycolate, vinylalcoholate,
propargylalcoholate, 2-ethyl-1-hexanolate; or R1' and/or
R2'=methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl,
iso-butyl, tert-butyl, n-pentyl, isopentyl, neo-pentyl,
tert-pentyl, hexyl, heptyl, n-octyl, iso-octyl,
2,2,4-trimethylpentyl, nonyl, decyl, dodecyl, n-dodecyl,
cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, o-tolyl,
p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl, benzyl, R2',
R3', R4'=independent, the same or different: 0, OH, methanolate,
ethanolate, n-propanolate, iso-propanolate, n-butanolate,
2-butanolate, iso-butanolate, tert-butanolate, n-pentanolate,
iso-pentanolate, neo-pentanolate, tert-pentanolate,
2-methyl-1-butanolate, hexanolate, heptanolate, n-octanolate,
iso-octanolate, 2,2,4-trimethylpentanolate, nonanolate, decanolate,
dodecanolate, n-dodecanolate, cyclo-pentanolate, cyclohexanolate,
cycloheptanolate, methylcyclohexanolate, glycolate, glycerate,
pinacolate neopentylglycolate, vinylalcoholate,
propargylalcoholate, 2-ethyl-1-hexanolate; or R1'=methyl, ethyl,
n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl,
n-pentyl, isopentyl, neo-pentyl, tert-pentyl, hexyl, heptyl,
n-octyl, iso-octyl, 2,2,4-trimethylpentyl, nonyl, decyl, dodecyl,
n-dodecyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl,
o-tolyl, p-tolyl, m-tolyl, xylyl, ethylphenyl, mesityl, phenyl,
benzyl, R2', R3', R4'=O, OH, methanolate, ethanolate,
n-propanolate, iso-propanolate, n-butanolate, 2-butanolate,
iso-butanolate, tert-butanolate, n-pentanolate, iso-pentanolate,
neo-pentanolate, tert-pentanolate, 2-methyl-1-butanolate,
hexanolate, heptanolate, n-octanolate, iso-octanolate,
2,2,4-trimethylpentanolate, nonanolate, decanolate, dodecanolate,
n-dodecanolate, cyclopentanolate, cyclohexanolate,
cycloheptanolate, methylcyclohexanolate, glycolate, glycerate,
pinacolate neopentylglycolate, vinylalcoholate,
propargylalcoholate, 2-ethyl-1-hexanolate; or R1', R2', R3',
R4'=independent, the same or different: O, OH, methanolate,
ethanolate, n-propanolate, iso-propanolate, n-butanolate,
2-butanolate, iso-butanolate, tert-butanolate, n-pentanolate,
iso-pentanolate, neo-pentanolate, tert-pentanolate,
2-methyl-1-butanolate, hexanolate, heptanolate, n-octanolate,
iso-octanolate, 2,2,4-trimethylpentanolate, nonanolate, decanolate,
dodecanolate, n-dodecanolate, cyclopentanolate, cyclohexanolate,
cycloheptanolate, methylcyclohexanolate, glycolate, glycerate,
pinacolate neopentylglycolate, vinylalcoholate,
propargylalcoholate, 2-ethyl-1-hexanolate. Especially preferred
according to the invention are mixtures with the following examples
of compound II: Isobutylisopropyl dimethoxysilan, diisopropyl
dimethoxysilan, diisbbutyldimethoxysilan, dicyclopentyl
dimethoxysilan, n-propyltrimethoxysilan, isobutyl-sec.-butyl
dimethoxysilan, cyclohexylisobutyl dimethoxysilan,
cyclo-pentylisobutyl dimethoxysilan, di-sec.-butyl dimethoxysilan,
dicyclohexyl dimethoxysilan, isobutylmethyl dimethoxysilan.
[0049] Mixtures of compound I with one or more of the following
examples of compound II of formula II are according to the
invention preferred (X.dbd.Cl or Br or I, with m=1): R1'=NH.sub.4,
Li, Na, K, Rb, for m=2: R1'=Cs, Mg, Ca, Sr, Ba, Zn for m=3: R1'=B,
Al, Sc, Y, for m=4: R1'=Ti, Zr, Hf.
[0050] Also, mixtures of compound I with one or more of the
following examples of compound II of formula III are according to
the invention preferred, such as: NaClO.sub.2, KClO.sub.2,
HClO.sub.2, HClO.sub.3, KClO.sub.3, NaClO.sub.3, HClO.sub.4,
NaClO.sub.4, KClO.sub.4, and, particularly preferred, NaCl, AIC13,
KCl, NaBr, KBr, NaClO.sub.4 and KClO.sub.4 and their respective
hydrates.
[0051] Moreover, mixtures of compound I with one or more of the
following examples of compound II of formula III are according to
the invention preferred (X.dbd.S): Na.sub.2SO.sub.4,
K.sub.2SO.sub.4, MgSO.sub.4, CaSO.sub.4, SrSO.sub.4, BaSO.sub.4,
Al.sub.2(SO.sub.4).sub.3, NaAl(SO.sub.4).sub.2,
NH.sub.4Al(SO.sub.4).sub.2, KAl(SO.sub.4).sub.2 and their hydrates,
particularly preferred are Al.sub.2(SO.sub.4).sub.3,
NaAl(SO.sub.4).sub.2, NH.sub.4Al(SO.sub.4).sub.2.
[0052] The molar ratio of compound I to compound II may by
advantage be 1:0.001 to 1:200, preferred is a ratio of 1:0,01 to
1:20.
[0053] The composition of compound I and/or compound. II may
contain suspension agents or solvents to improve reaction kinetics
and yield.
[0054] The invention further provides a process for the continuous
or batchwise catalysis of esterification, transesterification,
polyesterification, polytransesterification reactions of an alcohol
and an acid or acid derivative, e.g. an ester, anhydride or
halogenide, characterized by employing a catalytic composition as
defined above. This process may include the steps: [0055]
Preparation of a reaction mixture containing a polyvalent alcohol
and an acid or ester with at least two carboxy groups. [0056]
Addition of catalytic composition according to the invention.
[0057] At least two catalytic compounds I and II may be added to
the reaction mixture in isolated form, as solid, dissolved in a
suitable solvent, as a liquid or as suspension.
[0058] The employed carboxylic acid may be a monocarboxylic acid,
di- or polycarboxylic acid. Among dicarboxylic acids, carboxylic
acids containing at least two carboxyl groups, dicarboxylic acids
such as e.g. terephthalic acid and/or 2,6-naphthalenedicarboxylic
acid, isophthalic acid, 1,4-cyclohexane dicarboxylic acid,
1,6-naphthalene dicarboxylic acid, 4,4-bisphenyl dicarboxylic
acids, adipic acid, phthalic acid, alkane dicarboxylic acids,
halogen derivates of the mentioned dicarboxylic acids for example
tetrabromo phthalic acid, and copolymers of the mentioned
dicarboxylic acids or the esters of the mentioned carboxylic acids
for example dimethyl terephthalate, bis(hydroxyethyl)
terephthalate, 2,6-dimethyl naphthalate, 1,6-dimethyl naphthalate
are particularly preferred.
[0059] The alcohols employed in the process according to the
invention may be mono-, di- or polyvalent.
[0060] As di- or pblyvalent alcohols, alcohols such as ethylene
glycol, 1,3-propanediol, 1,4-butanediol and/or
1,4-cyclohexanedimethanol, di-, triethylene glycol, polyglycols
with a molecular weight below 1000 or neopentyl glycol, are
particularly preferred.
[0061] Further, recycled polyester material might be used as
co/monomer within the process based on the invention.
[0062] The inventors have shown that compound II, bearing a
heteroatom as such neither catalyzes the esterification, nor
transesterification, nor the polycondensation reaction.
Surprisingly, an unexpected synergism between the metal catalyst
(compound I) and the heteroatom compound (compound II) was found.
The catalytic activity of selected systems of compound I can be
increased according to the invention by approx. 50%.
[0063] According to the invention, the polycondensation is
catalyzed and accelerated by a new compound system. It has been
shown that in comparison to conventional catalytic systems less
amounts of catalyst and stabilizer lead to comparable results.
Furthermore, even high-viscous polyesters can be manufactured in a
direct process in by far shorter polycondensation times. The novel
mixtures according to the invention are further hydrolysis
resistant and may be added either during the esterification phase
and/or the precondensation phase as an active composition.
[0064] The catalytic composition of the invention shows a lower
toxicity in comparison with conventional catalytic systems.
[0065] The preferred metal concentration of the catalytically
effective metal compound (compound I) is 0.1 to 500 ppm (as Sn), in
particular 10-200 ppm (as Sn) in relation to the acid or ester to
be reacted.
[0066] The preferred concentration of the heteroatom containing
compound (compound II) is 0.0001 ppm (as compound) to 1%, in
particular 10-200 ppm in relation to the acid or ester to be
reacted.
[0067] Particularly preferred is a process for a polyesterification
reaction as defined above, characterized by reacting a dicarboxylic
acid or a dicarboxylic acid derivative with a divalent alcohol.
[0068] Particularly preferred derivatives of mono-, di-, or
polycarboxylic acids are esters or halogenides.
[0069] In the process of the invention hydroxycarboxylic acids such
as p-hydroxybenzoic acid, salicylic acid, lactic acid, glycol acid
or preferredly, derivatives thereof such as esters or ethers, and
their co-polyesters with dicarboxylic acids and/or diols as
described above may be reacted to the respective polyesters.
[0070] As a further compound a polyfunctional alcohol can be added
to the reaction mixture. The polyfunctional alcohol, such as
pentaerythritol can be added favored in a concentration of 0-500
ppm, in particular 50 ppm. The alcohol can be added together with
compound I or separately, simultaneously, before or after, latest
during the precondensation of the polyester. No influence on the
effect of the other compounds occurs in this case.
[0071] The compounds I and/or II used for the production of
polyester can be added during the period before the beginning of
the esterification and/or transesterification until shortly before
the end of the polycondensation, favored during the esterification
and/or transesterification or before the precondensation.
[0072] A solvent or suspending agent may be added to compound I
and/or compound II.
[0073] As solvents or suspending agents for the compounds I and/or
II a mono-, di- or polyvalent alcohol such as e.g. an alkanediol
may be employed. Preferred are 1,2-ethanediol, 1,3-propanediol,
1,4-butanediol, 2,2-dimethylpropan-1,3-diol.
[0074] The same solvent and/or suspending agent may be employed
during manufacturing of the catalytic composition and said
esterification, transesterification, polyesterification or
polytransesterification reaction.
[0075] Alternative to this, also a different solvent and/or
suspending agent may be employed during manufacturing of the
catalytic composition and said esterification, transesterification,
polyesterification or polytransesterification reaction.
[0076] Moreover, a solvent or suspending agent may be employed in
the manufacturing step of the catalytic composition being selected
from the group of mono-, di- or polyvalent alcohols that is reacted
in said esterification, transesterification, polyesterification or
polytransesterification reaction.
[0077] Further an organic liquid may be employed as solvent or
suspending agent for the catalytic composition that is indifferent
with respect to the polyester production process. Indifferent
organic liquids are e.g. alkanes, cycloalkanes or benzene
derivatives (for example benzene, toluene, xylenes). Also water or
a mixture of water with an alcohol or a polyvalent alcohol is
suited as solvent and/or suspending agent according to the
invention.
[0078] Further additives for a color correction such as cobalt
salts or organic dyes or pigments might be added to the reaction
mixture, usually in amounts of 0.00001-5% by weight with respect to
the acid or ester to be reacted.
[0079] Subject of the invention are further polycondensation
products, produced by the described process of esterification,
transesterification, polyesterification, polytransesterification
with the use of the catalytic compositions according to the
invention.
[0080] Furthermore, subject of the invention are polyester for
bottles, films, foils, yarn, molded padding, resins for powder
coatings and technical synthetic materials, obtainable by the
process according to the invention.
[0081] The polyester available by the process according to the
invention shows comparable qualities for the processability in
comparison with conventional polyesters for example catalyzed by
antimony. In comparison with usual high-viscous melt
polymerisations, resins produced with the compounds described in
the invention show a relatively low content of acetic aldehyde. In
particular the polyesters synthesized with the process according to
the invention show a narrow molecular weight distribution, a high
translucency and give a polymer with a high, desired blue shift. A
polymer of high viscosity is, unlike the state of the art using Sb
catalysts, obtained without difficulty.
[0082] In the case of the inventive use of compound I with
R1=--X-R.sup.A the organotin catalyst is incorporated into the
polymer by the means of an ester bond, that means the organotin
species can only be released out of the polymer resin by its total
destruction.
[0083] The polymers, produced with catalysts based on the invention
show a high blue shift (negative b-values; color values are
determined by using the CIE-Lab 100 color system with spectral
reference beam color measuring instrument LUCI 100, Dr. Lange).
[0084] Polyesters, produced according to the invention employing a
catalytic composition according to the invention show less
by-products such as acetic aldehyde in polyethylene terephthalate
(PET) in comparison with conventional techniques.
[0085] The polyesters produced according to the process described
in the invention are made by esterification or transesterification
with the use of the composition of compound I and/or compound II
described in the invention and optionally subsequent
polycondensation.
[0086] Preferred polyesters according to the invention are a)
polyethylene terephthalate (PET), containing 0.1-10 mass %
di-ethylene glycol and 0-10 mass % of isophthalic acid,
2-hydroxyisophthalic acid, p-hydroxyisophthalic acid,
2,6-naphthalene dicarboxylic acid and/or 1,4-cyclohexane
dimethanole as co-monomer; b) polyester for powder coatings mainly
poly-2,2-dimethylpropyl-1,3-terephthalate; c) polypropylene
terephthalate (PPT); d) polyester polyols as for example
polydiethyleneglycol terephthalate; e) polybutylene terephthalate
(PBT); f) polynaphthalene terephthalates (PNT), g) polyethylene
naphthalate (PEN).
[0087] The following examples further illustrate the invention
without, however, limiting the invention. Unless otherwise
indicated, parts and percentages relate to the weight, as in the
remainder of the description.
EXAMPLES
Example 1
Preparation of Catalytic Active Mixtures of compound I and compound
II
Apparatus:
[0088] 100 ml round bottom flask, magnetic stirrer, rotary
evaporator.
[0089] Starting Materials, Quantities: TABLE-US-00001 butyltin
tris[neodecanoate] 68.44 g [0.10 mol] a)triphenylphosphine 26.23 g
[0.10 mol] b)triphenylphosphite 31.03 g [0.10 mol]
c)triphenylphosphinoxide 27.83 g [0.10 mol] d)tributylphosphite
25.03 g [0.10 mol]
Preparation:
[0090] The heteroatom compound II, dissolved in xylene (ethanol in
the case of triphenylphosphine oxide) was given into the round
bottom flask and stirred for 15 min. Butyltin tris[neodecanoat]
dissolved in 50 ml xylene or ethanol, respectively was added to the
mixture by the means of a tap funnel and stirred for an additional
hour. The catalytic active system was obtained after removal of the
solvent under reduced pressure.
Analysis:
[0091] .sup.119Sn-NMR [0092] .sup.31P-NMR [0093] catalyst system e)
Apparatus:
[0094] 250 ml three necked round bottom flask, tap funnel, magnetic
stirrer, water separator, rotary evaporator.
[0095] Starting Materials, Quantities: TABLE-US-00002 monobutyltin
oxide 20.88 g [0.10 mol] neodecanoic acid 34.6 g [0.20 mol]
triphenylphosphine 26.23 g [0.10 mol]
Synthesis:
[0096] Monobutyltin oxide was dissolved in 150 ml xylene,
triphenylphosphine, dissolved in 50 ml xylene and neodecanoic acid
were added within 10 min. The mixture was heated under reflux until
the water-formation stops. The product was obtained after
filtration and removal of the solvent under reduced pressure.
Example 2
Catalyst Test by Synthesis of a Resin for Powder Coatings
[0097] Starting Materials, Quantities: TABLE-US-00003 terephthalic
acid 83.07 g [0.50 mol] neopentylglycol 104.15 g [1.00 mol]
(2,2-Dimethyl-1,3-propandiol) catalyst: 0.05%[m/m] calculated as
Sn.
Synthesis:
[0098] Catalyst, neopentyl glycol and terephthalic acid were given
into a 250 ml three-necked round bottom flask. The mixture was
heated to a maximum by the means of a heating jacket, the reaction
water is distilled off and the amount formed is metered. The
reaction time equals the time between the first water formation and
the "clear point" of the reaction.
Example 3
Catalyst Test by Synthesis of a Resin for Powder Coatings with
Physical Mixtures of Monobutyltin Oxide, Triphenylphosphine and
Triphenylphosphite
[0099] Starting Materials, Quantities: TABLE-US-00004
terephthalicacid 83.07 g [0.50 mol] neopentylglycol 104.15 g [1.00
mol] (2,2-Dimethyl-1,3-propandiol) catalyst: f) 0.165 g
monobutyltin oxide, 0.207 g triphenylphosphine g) 0.165 g
monobutyltin oxide, 0.245 g triphenylphosphite
Synthesis:
[0100] Catalyst, neopentyl glycol and terephthalic acid are given
into a 250 ml three-necked round bottom flask. The mixture is
heated to a maximum by the means of a heating jacket, the reaction
water is distilled off and the amount is metered.
[0101] The reaction time equals the time between the first water
formation and the "clear point" of the reaction.
[0102] Table 1 shows the acceleration of the reaction time in the
described resin synthesis with the mixtures of (comparative)
examples 1a, 1b, 1c, 1d, 1e and 1f, 1g in comparison with the
uncatalized reaction or with monobutyltinoxide (0,05%[m/m]) as
catalyst. TABLE-US-00005 TABLE 1 reaction time of the mixtures a-g.
Sn- volume H.sub.2O [ml]: catalyst content 15 30 45 60 75 90 [min]
(0.05% tin) [%] min min min min min min 105 min 120 min 135 min 150
min 165 min 180 min time remarks without 1 1 2 3 4 300 aborted
catalyst triphenylphosphine 0.05 3 4 4.5 300 aborted monobutyltin
0.05 9 14 23.5 155 clear, oxide colorless monobutyltin 0.05 2.5 4
5.5 7 9.5 11 13 15 17 18.5 21 22 180 hazy, trineodecanoate
colorless a 0.05 3.5 6 9 11 14 16 100 clear, colorless b 0.05 2.5 7
9 12 15 17 100 clear, colorless c 0.05 2 6 9 13 15 18 97 clear,
colorless d 0.05 4 8 12 16 19 85 clear, colorless e 0.05 5 8 12 16
18 60 clear, colorless f 0.05 8 14 16 100 clear, colorless g 0.05 4
6 8 10 14 14 16 16 120 clear, colorless
Example 4
Polycondensation of bis(2-hydroxyethyl) terephthalate (BHET)
Experimental Method:
[0103] Polycondensation equipment 1 (glass equipment) for the melt
polycondensation of BHET [0104] Tempering-bath (salt bath),
polycondensation vessel (glass), screw mixer (glass), vacuum pump,
pressure gauge
[0105] As a polycondensation equipment, a round glass flask with
round bottom was used, (internal diameter 2,6 cm, and 35 cm height,
described in T. Johnson, Chem. Fibers International 46 (1996) 280;
49 (1999) 455). A horizontal vapor outlet was integrated into the
upper third of the flask wall. A further extension tube near the
bottom of the vessel allowed sampling from the polymer melt. The
stirrer was a glassware screw mixer, reaching down to the ground
(1,8 cm diameters). The mixer was operated with a rotation speed of
100 min.sup.-1 and intermixed the melt with axially downward
direction.
[0106] 25,4 g (0,1 mol) BHET was filled into the polycondensation
vessel, the catalyst (5 to 200 ppm as metal) was added and the
vessel locked. Then the polycondensation vessel filled with the
reaction mixture was evacuated three times and rinsed with dry
nitrogen before it was immersed in the tempering-bath. The bath
temperature was preset so that the desired internal temperature of
280.degree. C. was reached in the polycondensation vessel. After
the reaction mixture was melted, the stirrer was started and the
vessel evacuated within 15 min onto a vacuum of 2.times.10.sup.-1
mbar. The time of the first formation of glycol at the wall of the
glass was regarded as t.sub.0. The attainable final pressure for
this equipment of approximately 4 to 5.times.10.sup.-2 mbar, was
reached after approx. 1 h experimental time, depending on the
progress of the polycondensation. Through the sampling device
samples could be taken by means of a VA steel wire, maintaining a
nitrogen counterflow. At the end of the reaction up to 5 g could be
taken from the vessel for further analysis. During the
polycondensation, an average sampling required one minute, from
breaking the vacuum to re-applying the vacuum. At the end of the
polycondensation sampling was done within two minutes after
aerating the vacuum.
PET Characterization
[0107] The determination of the intrinsic viscosities was performed
as follows:
[0108] The relative solution viscosities .eta..sub.rel for PET were
determined in phenol (3 parts)/dichlorobenzene (2 parts) mixtures
using 0.5 percent solutions at 25.degree. C. The conversion of the
relative solution viscosities into the intrinsic viscosity [.eta.]
was done according to BILLMEIER. .eta. intr = 1 4 .times. .eta. rel
- 1 c + 3 / 4 .times. ln .eta. rel c ##EQU1##
[0109] From the intrinsic viscosities (IV) the average molecular
weights Mn (number average) as well as the degrees of
polymerization P.sub.n were calculated. For PET applies:
Mn=(1000.times.IV).sup.1,5186; Pn=Mn/192.
[0110] The absolute viscosities were measured using the
viscosimeter AVS 250 and the tempering-unit CT 1450 of Schott
Gerate GmbH. Comparison measurements between different laboratories
gave matching results.
[0111] The color values were determined using the
CIE-LAB-Farbsystem (color system) by the spectral reference beam
color measuring instrument LUCI 100, Dr. Lange.
[0112] The device STA 625 of Polymer Laboratories was used for TG
and DSC-measurements.
[0113] The COOH end groups were determined by potentiometric
titration of a cresol solution of the polymers with diluted aqueous
NaOH.
[0114] BHET and the catalyst were introduced into the reaction
vessel and rinsed well with nitrogen.
[0115] The reaction vessel was placed into the salt bath. Recording
of reaction time started now. Within 15 min the pressure was
lowered from 100 mbar to 0,09 mbar. At the end of the reaction a
pressure of 0,04 mbar was reached.
[0116] The following table 2 shows the results of the
polycondensation experiments for the catalyst e in comparison to
Sb- and Ti-based catalysts (table 3). Criteria of the catalyst
activity are the attainable molar mass in specific time periods,
the increasing influence of the thermal degradation, recognizable
by the flattening of the P.sub.n-t-function as well as the color
values of the polyester. The amount of the evolved ethanal
(acetaldehyde) that directly correlates with the degree of thermal
ester group cleavage is a further essential criterion of the
catalyst suitability. The color values in the tables show the
discoloration of the product, the a-values representing
green/red-gradients and the b-values representing
blue/yellow-gradients. Negative a-values correspond to green,
negative b-values correspond to blue gradients. Blue shift is
favored technologically. TABLE-US-00006 TABLE 2 Polycondensation of
BHET with catalyst e. color values using the time Sn COOH M.sub.n
CIE-LAB-system [min] [ppm] .eta..sub.l [.mu.eq/g] [g/Mol] P.sub.n L
a b 30 123 0.2764 16 5104 26 34.19 -0.15 -0.14 60 123 0.5216 14
13386 69 33.84 -0.28 0.46 90 123 0.7152 19 21616 112 37.73 -0.44
1.05 120 123 0.8399 24 27588 143 36.54 -0.63 1.78
[0117] TABLE-US-00007 TABLE 3 Polycondensation of BHET with Sb and
Ti catalysts. temperature time catalyst conc. Catalyst [.degree.
C.] [min] [ppm] P.sub.n antimony 270 30 190 25 triacetate antimony
270 60 190 45 triacetate antimony 270 90 190 65 triacetate antimony
270 120 190 85 triacetate antimony 270 150 190 100 triacetate
antimony 270 180 190 115 triacetate antimony 280 30 190 30
triacetate antimony 280 60 190 55 triacetate antimony 280 90 190 75
triacetate antimony 280 120 190 95 triacetate antimony 280 150 190
115 triacetate antimony 280 180 190 135 triacetate tetrabutyl
titanate 280 30 20 45 tetrabutyl titanate 280 60 20 65 tetrabutyl
titanate 280 90 20 85 tetrabutyl titanate 280 120 20 105 tetrabutyl
titanate 280 150 20 125 tetrabutyl titanate 280 180 20 150
[0118] The comparative investigations for the catalytic activity of
the selected tin compounds show that no noteworthy thermal
decomposition is to be expected within 2 h of polycondensation time
at temperatures of 280.degree. C. Therefore it is absolutely
possibly to synthesize even higher molecular weight polyethylene
terephthalates by prolongation of the polycondensation time.
[0119] All examined tin compounds proved as high-activity catalysts
for the polycondensation of BHET, which show significantly higher
activity than stibious compounds. Their polytransesterification
activity is superior to titanium alkoxides and titanium chelates.
If required, they can be employed also in higher
concentrations.
* * * * *