U.S. patent application number 09/272044 was filed with the patent office on 2002-08-01 for process for the production of telechelic substances, telechelic substances produced in this manner and use thereof.
Invention is credited to HOCKER, HARTWIG, KEUL, HELMUT, MARGOTTE, DIETER, MELCHIORS, MARTIN, NEUMANN, ANDREAS.
Application Number | 20020103320 09/272044 |
Document ID | / |
Family ID | 7862419 |
Filed Date | 2002-08-01 |
United States Patent
Application |
20020103320 |
Kind Code |
A1 |
MELCHIORS, MARTIN ; et
al. |
August 1, 2002 |
PROCESS FOR THE PRODUCTION OF TELECHELIC SUBSTANCES, TELECHELIC
SUBSTANCES PRODUCED IN THIS MANNER AND USE THEREOF
Abstract
A novel process for the production of oligomeric and polymeric
telechelic compositions, to the telechelic compositions produced in
this manner and to use thereof in the plastics, fibers or lacquer
sectors.
Inventors: |
MELCHIORS, MARTIN;
(LEVERKUSEN, DE) ; MARGOTTE, DIETER; (KREFELD,
DE) ; HOCKER, HARTWIG; (AACHEN, DE) ; KEUL,
HELMUT; (AACHEN, DE) ; NEUMANN, ANDREAS;
(AACHEN, DE) |
Correspondence
Address: |
PATENT DEPARTMENT
BAYER CORPORATION
100 BAYER ROAD
PITTSBURGH
PA
152059741
|
Family ID: |
7862419 |
Appl. No.: |
09/272044 |
Filed: |
March 18, 1999 |
Current U.S.
Class: |
526/319 ;
525/326.2; 525/328.2; 526/135; 526/145; 526/146; 526/147; 526/220;
526/92 |
Current CPC
Class: |
C08F 4/40 20130101 |
Class at
Publication: |
526/319 ; 526/92;
526/135; 526/145; 526/146; 526/147; 526/220; 525/326.2;
525/328.2 |
International
Class: |
C08F 118/02 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 26, 1998 |
DE |
198 13 353.7 |
Claims
1. A process for making a telechelic composition the formula:
Y.sup.1--Q--Y.sup.2, wherein q represents an oligomeric, optionally
substituted, hydrocarbon residue with a molecular weight
300<Q<1000 of the formula 6wherein n is an integer in the
range 3.ltoreq.n.ltoreq.500, each R', R", R'" comprise a component
selected from the group consisting of h, a C.sub.1-C.sub.20
(cyclo)alkyl, a C.sub.6-C.sub.24 aryl, halogen, CN, a
C.sub.1-C.sub.20 alkyl ester, an alkylamide, a C.sub.6-C.sub.24
aryl ester and arylamide, aldehydes, keto groups, ether groups, or
wherein each R', R", R'" is a constituent of a ring comprisinga
component selected from the group consisting of cyclic anhydrides,
cyclic imides, cyclic alkanes and wherein Y.sup.1 and Y.sup.2 are
functional groups that are identical or different; wherein the
process comprises polymerization of: A) a monomer component
comprising free-radically polymerizable, ethylenically unsaturated
monomers of the formula R'HC.dbd.CR"R'", in which R', R", R'" have
the above stated meaning and which contain no groups Y.sup.1,
Y.sup.2 in the molecule, or a mixture of such monomers with B) an
initiator component, C) a transition metal component, and D) one or
more complex ligands which are capable of complexing the central
atom(s) of the compound C, characterized in that polymerization is
performed in the presence of E) a functionalizing reagent which has
at least one C.dbd.C double bond and at least one of the desired
functional groups Y.sup.1, Y.sup.2.
2. The process of claim 1, wherein the compound Y.sup.1--Q--Y.sup.2
has molecular weight 500<M.sub.n<10000, where Y.sup.1 and
Y.sup.2 each comprise a component selected from the group
functional groups consisting of isocyanate-reactive compounds,
alcohol-reactive compounds, carboxylic acid-reactive compounds and
epoxide-reactive compounds, and wherein the proces comprises the
polymerization of: A) a monomer component comprising free-radically
polymerizable, ethylenically unsaturated monomers of the formula
R'HC.dbd.CR"R'", in which R', R", R'" have the above-stated meaning
and contain none of the functional groups Y.sup.1, Y.sup.2, or a
mixture of such monomers, B) an initiator component comprising a
compound R.sup.1R.sup.2R.sup.3C--X, which contains one or more
free-radically abstractable or transferable atoms or groups of
atoms X, in which R1 represents either X or a linear or branched
alkyl redidue which is substituted either with X or with Y1 and
optionally further residues, and R2, R3 mutually independently
represent hydrogen or optionally substituted, linear or branched
aliphatic or aromatic hydrocarbon residues or electron-attracting
substituents such as COOR, CN, NO.sub.2, COCl, CONHR, CONR.sub.2 or
COR, C) a transition metal component comprising a compound
M.sub.pZ.sub.q, which Cu, Fe, Ru, Cr, Mo, Wo, Mn, Rh, Re, Co, Ni,
V, Zn, Au, Ag oder Sm, wherein M may be present in the transition
metal compound in different oxidation states and may participate in
a reversible redox process, and an anion Z from the group
comprising halide, hydroxide, C.sub.1-C.sub.6 alkoxy,
SO.sub.4.sup.2-, PO.sub.4.sup.3-, R.sup.4PO.sub.4.sup.2-,
R.sup.4R.sup.5PO.sub.4.sup.-, R.sup.3R.sup.4R.sup.5P--,
CF.sub.3COO--, PF.sub.6.sup.-, CH.sub.3SO.sub.3.sup.-,
ArSO.sub.3.sup.-, CN.sup.- or R.sup.4COO.sup.-, wherein R.sup.4,
R.sup.5 mutually independently represent hydrogen or an optionally
aryl- or halo-substituted alkyl residue, and wherein p and q are
determined by the valencies of M and Z in the transition metal
compound and D) a mono- or polydentate complex ligand L, which
contains one or more nitrogen, oxygen, sulphur or phosphorus atoms
and may combine with at least one cation of the metal M to form
complexes, characterized in that components A) to D) are reacted in
a living free-radical polymerization reaction to yield the
telechelic substance Y.sup.1--Q--Y.sup.2 in the presence of E) a
compound R.sup.6R.sup.7C.dbd.CR.sup.5(R.sup.9--Y.sup.2), which
contains at least one olefinic double bond and at least one
functional group Y.sup.2 reactive towards isocyanates, alcohols,
carboxylic acids or epoxides, wherein a carbon residue R.sup.9 must
be present between the double bond and Y.sup.2, which carbon
residue R.sup.9 represents a linear or branched, optionally
substituted alkyl chain having a minimum length of 1 methylene
group, and wherein R.sup.6, R.sup.7 and R.sup.8 mutually
independently represent hydrogen or an optionally aryl- or
halo-substituted alkyl residue.
3. The process of claim 1, wherein component B comprises a compound
having the formula R.sup.1R.sup.2R.sup.3C--X, wherein R.sup.1 has
the formula Y.sup.1--R.sup.10, wherein R.sup.10 represents a linear
or branched hydrocarbon residue with 1-10 carbon atoms and
optionally substituted with aromatic residues, which hydrocarbon
residue may optionally also contain ether, ester, amide, urethane
or urea groups, and may additionally also contain linear polymeric
blocks, such as polyether blocks, polyester blocks or polyacrylate
blocks, and wherein Y.sup.1 comprises a component selected from the
group consisting of --OH, --Cl, --COOH, --COOR, --CN, --NO.sub.2,
--SO.sub.3H, --COCl, --CONHR, --CONR.sub.2, --OR, --OP(.dbd.O)R,
--OP(.dbd.O)(OR), --OP(.dbd.O)(OR).sub.2 or --C(.dbd.O)R, wherein
R.sup.2, R.sup.3 have the above-stated meaning.
4. The process of claim 1, wherein component B comprises a
component selected from the group consisting of compounds having
the formulae 7wherein Hal=Cl or Br, R.sup.3=C.sub.1-C.sub.6 alkyl,
R.sup.14=H or CH.sub.3, n=1-10 and m=1-225.
5. The process of claim 1, wherein component B comprises a compund
having the formula R.sup.1R.sup.2R.sup.3C--X, which contain no
functional groups Y.sup.1, wherein R.sup.1 is identical to X or has
the formula X--CR.sup.10R.sup.11R.sup.12, wherein R.sup.2, R.sup.3
and R.sup.10 have the above-stated meaning and R.sup.11 und
R.sup.12 mutually independently represent hydrogen or optionally
substituted, linear or branched aliphatic or aromatic hydrocarbon
residues.
6. The process of claim 1, wherein the component B comprises a
component selected from the group consisting of compounds having
the formulae 8wherein Hal=Cl or Br, R.sup.13=C.sub.1-C.sub.6 alkyl,
R.sup.14=H or CH.sub.3, n=1-225 und m=2-6.
7. The process of claim 1, wherein the component A comprises a
component comprising a compound selected from the group consisting
of butyl acrylate, 2-ethylhexal acrylate, methyl methacrylate,
butyl methacrylate, cylohexyl methycrylate, isobornyl methacrylate,
butyl methacrylate, cyclohexyl methacrylate, isobornyl
methacrylate, maleic anhydride or styrene, and mixtures
thereof.
8. The process of claim 1, wherein component C comprises a
component comprising a compund selected from the group consisting
of CuCl, mixtures of CuCl and CuCl.sub.2, CuBr, and mixtures of
CuBr and CuBr.sub.2.
9. The process of claim 1, wherein component D) comprises a
compound selected from the group consisting of compounds having the
formula 9wherein R.sup.15 bis R.sup.18 mutually independently
represent hydrogen or C.sub.1-C.sub.20 aliphatic or
C.sub.6-C.sub.24 aromatic hydrocarbon residues, and R.sup.15 bis
R.sup.18 may optionally also be linked together to form an
unsaturated, optionally aromatic, ring containing nitrogen, and
wherein component D may also be attached to a polymer or
incorporated into a polymer chain by means of one or more of
residues R.sup.15 to R.sup.18.
10. The process of claim 1, wherein component E comprises a
component selected from the group consisting of 10wherein R.sup.19
is hydrogen or a linear or branched C.sub.1-C.sub.6 alkyl chain and
R.sup.20 and R.sup.21 is a hydrocarbon residue, R.sup.22 is
hydrogen or an alkyl residue, preferably methyl, n may be 1-4 and m
may be 1-10.
11. The process of claim 1, wherein component E comprises a
compound selected from the group consisting of 2-propen-1-ol,
3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, and the corresponding
propoxylated compounds obtained by addition of 1-10 mol of
propylene oxide onto the OH group is used.
12. The process of claim 1, wherein the complex ligand D is used
relative to the transition metal compound C at a molar ratio of D:C
of 2.5:1 to 3.1 and the initiator coumpound B is present relative
to the transition metal compound C at a molar ratio of B:C of 1:1
to 3:1 and component E is used in a quantity corresponding to a
molar ratio of C.dbd.C double bonds in component E to transferable
atoms/groups of atoms X in component B of least 3:1.
13. The telechelic composition obtainable according to claims
1.
14. The telechelic composition of claim 13, wherein the composition
has a number average molecular weight of between 1000 and 5000.
Description
FIELD OF THE INVENTION
[0001] The invention relates to a novel process for the production
of oligomeric and polymeric telechelic substances, to the
telechelic substances produced in this manner and to the use
thereof in the plastics, fibers or lacquer sectors.
BACKGROUND OF THE INVENTION
[0002] Telechelic substances are generally defined as linear
oligomers or low molecular weight linear polymers having functional
groups on both chain ends. A comprehensive review of the production
of telechelic substances may be found, for example, in Adv. Polym.
Sci. 81, 168 (1987). They are significant, inter alia, as additives
and as structural units (prepolymers) for copolymers having a
defined structure (e.g., block copolymers, comb polymers, star
polymers). When used as structural units in copolymers, telechelic
substances must be as precisely bifunctional as possible.
[0003] The best known reactions for the production of telechelic
substances which have a functionality of exactly two are (1)
polyaddition reactions (for example, to yield polyurethanes or
polyureas), (2) polycondensation reactions (for example, to yield
polyesters, polycarbonates, or polyamides) as well as (3)
ring-opening anionic or cationic polymerization reactions of
heterocyclic monomers (for example, cyclic esters, carbonates,
acetals or ethers), optionally with terminating reagents containing
the desired functional groups.
[0004] Telechelic polyacrylates, i.e. low molecular weight acrylate
polymers having two defined functional end groups which can
participate in crosslinking, chain extension and/or coupling
reactions conventionally used in lacquer chemistry are of great
interest for use in the lacquer industry
[0005] Telechelic polyacrylates, however, cannot be produced using
any of the above-stated processes.
[0006] Various methods are known in polymer chemistry for
incorporating functional end groups into polyvinyl or polyacrylate
compounds, for example, oxidative chain scission (e.g., with
oxygen, ozone, osmium or ruthenium tetroxide). However, these
methods are non-specific and/or require the presence of double
bonds in the polymer chains as a point of attack for scission. It
is virtually impossible to achieve exact bifunctionality with these
methods.
[0007] If monomers having the desired functional group are used in
a free-radical polymerization in a quantity calculated to yield a
functionality of two, a product mixture is obtained having an
average functionality of two. The product, however, contains not
only bifunctional molecules, but also tri- and more highly
functional molecules, monofunctional molecules as well as
non-functional polymer molecules.
[0008] If initiators and/or terminating reagents having the desired
functional groups (such as functionalized diazo compounds,
functionalized peroxides or redox initiators) are used instead of
the monomers having functional groups, a functionality of two is
generally not achieved because various termination reactions
co-occur, e.g. disproportionation, recombination, termination by
initiator radicals or termination by the terminating reagent.
[0009] In "dead and" polymerization, a large excess of an initiator
having the desired end group is used. In this technique, each
polymer chain can be terminated with an initiator molecule and is
accordingly bifunctional. However, only very low molecular weight
polymers are formed and large quantities of initiator are
required.
[0010] Telomerization (i.e., polymerization of vinyl or arcrylate
monomers in the presence of chain-transfer reagents having elevated
chain-transfer constants) also yields only low molecular weights
and this method is restricted to a few instances (e.g.,
Polymerization in the presence of tetrachloromethane,
dibromomethane or disulfides having functional groups). since it is
not entirely possible to suppress disproportionation as a
termination reaction between two active chain ends, telechelic
substances are obtained having functionalities of less than two. At
least in the case of the halogen compounds, it is also necessary to
perform a subsequent polymer-analogous reaction of the halogen
substituents to yield the desired functional groups.
[0011] Telechelic polymethacrylates may be produced by group
transfer polymerization with ketene silyl acetals, wherein the
functional groups are formed by transformation of the silyl groups.
Disadvantages of this method are (1) the requirement of high purity
monomers and solvents and (2) the price and availability of the
initiators which are needed, requirements which make such a process
useful only for special applications.
[0012] EP-A 613,910 and EP-A 622,378 disclose the production of
.alpha.-.omega.-polymethacrylate diols by selective
transesterification of the terminal ester group of an
.alpha.-hydroxy-functional polyalkyl methacrylate. This process has
various disadvantages. First, the .alpha.-hydroxy-functional
polyalkyl methacrylate is produced by free-radical polymerization
in the presence of large quantities of mercaptoethanol, a compound
which has a considerable odor nuisance. Second, the method is a
multi-stage, energy-intensive and time-consuming process; the
process involves the removal of the excess mercaptoethanol and the
solvent used by distillation, transesterification with an excess of
a diol in the presence of a catalyst, removal of the methanol by
distillation, repeated washing of the product to remove the
catalyst and excess diol as well as still further purification
stages. Third, this reaction is restricted solely to the use of
alkyl methacrylates, since the transesterification reaction
otherwise no longer proceeds sufficiently selectively on the
terminal ester group of the chain.
[0013] Another special technique which has a limited range of
applications and no economic potential is ring-opening
polymerization of unsaturated heterocyclics (for example, cyclic
ketene acetals, unsaturated spiroorthocarbonates); such monomers
are not industrialy avilable.
[0014] None of the methods so far mentioned is thus suitable for
the production of the desired telechelic polyacrylates, because the
desired functionality is not achieved, the method is restricted to
only a few specific cases and/or polymer-analogous subsequent
reactions are required. There is a need for a polymerization
process which combines ease of performance with good control of the
polymerization and in particular of the end groups of the polymer
chains. Living free-radical polymerization is one such process.
[0015] Living free-radical polymerization is a relatively recent
method for the performance of controlled free-radical
polymerization. It combines the advantages of conventional
free-radical polymerization (simple production process, low costs
and a wide range of monomers) with those of living polymerization
(polymers of a defined structure, molecular weight, molecular
weight distribution and end group functionality). In this process,
the objective of precise control of the free-radical polymerization
is achieved by reversible chain termination/blocking
("end-capping") after each growth stage.
[0016] The equilibrium concentration of the actively polymerizing
chain ends at this point is so low in comparison with the
equilibrium concentration of the blocked ("dormant") chain ends
that termination and transfer reactions are largely suppressed in
comparison with the growth reaction. since the end-capping is
reversible, all the chain ends remain "living" providing that no
terminating reagent is present. This allows control of the
molecular weight, a narrow molecular weight distribution and
purposeful functionalization of the chain end by terminatig
reagents.
[0017] Initial attempts at controlled free-radical polymerization
(using the iniferter method) were described, for example, in
Makromol. Chem., Rapid Commun. 3 (1982), 127 and 132. The iniferter
method here describes a class of free-radical initiators which can
enter into initiation, transfer and reversible termination
reactions, e.g., tetraalkylthiuram disulfides which are
photolytically cleaved and activated. In this manner, it is
possible to produce polymers having dithiocarbamate end groups and
which may be reactivated by irradiation.
[0018] U.S. Pat. No. 4, 581, 429 discloses the principle of
reversible chain termination by using free-radicals based in linear
or cyclic nitroxides such as tetramethyl-1-piperidinyloxy (TEMPO).
If this nitroxide is reacted with a reactive carbon radical capable
of initiating a free-radical vinyl polymerization reaction, a
reversibly cleavable C--O bond is formed which, when subjected to
moderate heating, is capable of bringing about polymerization by
insertion of vinyl monomers between the nitroxide and carbon
radical. After each monomer addition, the newly formed radical is
"scavenged" by the nitroxide; this reversibly blocked chain end may
then insert further monomer molecules. Functional end groups are
also described and in this case are obtained by
polymer-analogous.
[0019] This concept of reversible termination with nitroxide has
been developed into a practical polymerization method in, for
example, J. Am. Chem. Soc. 116, 11185 (1994), Macromolecules 28,
2993 (1995), U.S. Pat. Nos. 5,322,912, 5,401,804, 5,412,047 and
5,449,724; and WO 94/11412, WO 95/26987 and WO 95/31484. The
starter system used in this case is a combination of dibenzoyl
peroxide (BPO) and TEMPO.
[0020] Another approach is Atom Transfer Radial Polymerization
(ATRP), in which a transition metal complex compoundd ML, abstracts
a transferable atom or group of atoms X (for example, Cl and Br)
from an organic compound RX to form an oxidized complex compound
MLXX and an organic radical R.cndot., which undergoes an addition
reaction with a vinyl monomer Y to form the carbon radical
RY.cndot.. This radical is capable of reacting with the oxidized
complex compound, transferring X to RYX and ML.sub.x, which can
initiatae a new ATRP reaction and thus a further growth stage. The
actively polymerizing species RY.cndot. is thus reversibly blocked
by the abstractable group x with the assistance of the transition
metal compound, which makes the redox process possible (for
example, Macromolecules 28, 1721 (1995); Macromolecules 29, 1070
(1996), Macromolecules 28, 7970 (1995), WO 95/25765, WO 96/30421
and WO 97/18247).
[0021] It is an object of the invention to provide a process that
produces a homo- or copolymer having a purposefully established
molecular weight and narrow molecular weight distribution in a
single reaction stage from one or more vinyl monomers, in
particular, acrylate monomers and styrene.
[0022] It is an object of the invention to provide a process in
which the resultant polymers have two functional end groups which
are capable of further reaction or crosslinking with the functional
groups usual in lacquer chemistry.
[0023] The foregoing objects have been achieved by a process in
which telechelic substances may purposefully be produced by
free-radical (co)polymerization of olefinically unsaturated
monomers using the living free-radical polymerization method with
an initiator system, which optionally contains one of the desired
functional groups, in the presence of a functionalizing reagent,
which has the desired functional group and terminates the chains
once the monomers have been consumed.
SUMMARY OF THE INVENTION
[0024] The present invention relates to a process for the
production of oligomeric and polymeric telechelic substances of the
formula
Y.sup.1--Q--Y.sup.2
[0025] wherein
[0026] Q represents an oligomeric, optionally substitued
hydrocarbon residue with a molecular weight 300<Q<10000 of
the formula 1
[0027] in which n is an interger in the range 3.ltoreq.n.ltoreq.500
and R', R", R'" may mutually independently be H,
C.sub.1-C.sub.20-(cyclo)alky- l, C.sub.6-C.sub.24-aryl, Halogen,
CN, C.sub.1-C.sub.20-alkyl ester oder alkylamide, C.sub.6-C.sub.24
arylester or arylamide, wherein R', R", R'" may also contain
further functional groups such as, for exemple, aldehyde, keto or
ether groups and R' and R" may also be constituents of a ring, for
example, in a cyclic anhydride, cyclic imide or cyclic alkane and
the functional gropus Y.sup.1, Y.sup.2 may be identical or
different. the process involves the polymerization of:
[0028] A) free-radically polymerizable, ethylenically unsaturated
monomers of the formula
R'HC.dbd.CR"R'",
[0029] in which R', R", R'" have the above-stated meaning and
contain none of the functional groups Y.sup.1, Y.sup.2, or a
mixture of such monomers with
[0030] B) an initiator compound or a mixture of such compounds,
[0031] C) a transition metal compound or a mixture of compound
and
[0032] D) one or more complex ligands which are capable of
complexing the central atom(s) of the compound C, characterized in
that polymerization is performed
[0033] E) a functionalizing reagent which has at least one C.dbd.C
double bond and least one of the desired functional groups Y.sup.1,
Y.sup.2.
[0034] The present invention also provides the telechelic
substances obtainable using the process according to the
invention.
[0035] The present invention also provides the use of the
telechelic substances according to the invention as structural
units for plastics, adhesives or fibers and as a binder, binder
component or structural unit for binder components in coating
compositions and adhesives.
DETAILED DESCRIPTION OF THE INVENTION
[0036] A preferred process is for the production of oligomeric or
polymeric telechelic substances Y.sup.1--Q--Y.sup.2 of the
molecular weight 500<M.sub.n<10000, in which Q denotes an
oligomeric or polymeric, optionally substituted, hydrocarbon
residue as defined above with a molecular weight 300<Q<10000
and Y.sup.1, Y.sup.2 may be identical or different and represent
functional groups reactive towards isocyanates, alcohols,
carboxylic acids or epoxides, by polymerization of
[0037] A) free-radically polymerizable, ethylenically unsaturated
monomers of the formula in which R', R", R'" have the above-stated
meaning and contain none of the functional groups Y.sup.1, Y.sup.2
or a mixture of such monomers, which contain no groups Y.sup.1,
Y.sup.2 in the molecule, or a mixture of such monomers with
[0038] B) an initiator compound R.sup.1R.sup.2R.sup.3C--X, which
contains one or more free-radically abstractable or transferable
atoms or groups of atoms X, in which R.sup.1 represents either X or
a linear or branched alkyl residue which is substituted either with
X or with Y' and, optionally, further residues, and R.sup.2,
R.sup.3 mutually independently represent hydrogen or optionally
substituted, linear or branched aliphatic or aromatic hydrocarbon
residues or electron-attracting substituents such as COOR, CN,
NO.sub.2, COCl, CONHR, CONR.sub.2, or COR,
[0039] C) a transition metal compound M.sub.pZ.sub.q, which is
prepared from a cation of a metal M from the group comprising cu,
Fe, ru, Cr. MO, Wo, Mn, Rh, Re, Co, Ni, V, ZN, Au, Ag or Sm,
wherein M may be present in the transition metal compound in
different oxidation states and may participate in a reversible
redox process, and an anion Z from the group comprising halide,
hydroxide, C.sub.1-C.sub.6 alkoxy, SO.sub.4.sup.2-,
PO.sub.4.sup.3-, R.sup.4PO.sub.4.sup.2-,
R.sup.4R.sup.5PO.sub.4.sup.-, R.sup.3R.sup.4R.sup.5P--,
CF.sub.3COO--, PF.sub.6.sup.-, CH.sub.3SO.sub.3-, ArSO3.sup.-,
CN.sup.- oder R.sup.4COO.sup.-, wherein R.sup.4, R.sup.5 mutually
independently represent hydrogen or an optionally aryl- or
halosubstituted alkyl residue, and wherein p and q are determined
by the valencies of M and Z in the transition metal compound
and
[0040] D) a mono- or polydentate complex ligand L, which contains
one or more nitrogen, oxygen, sulphur or phosphorus atoms and may
combine with at least one cation of the metal M to form complexes,
characterized in that components A) to D) are reacted in a living
free-radical polymerization reaction to yield the telechelic
substance Y.sup.1--Q--Y.sup.2 in the presence of
[0041] E) a compound R.sup.6R.sup.7C.dbd.CRW(R.sup.9--Y.sup.2),
which contains at least one olefinic double Y2 bond and at least
one functional group Y reactive towards isocyanates, alcohols,
carboxylic acids or epoxides, wherein a carbon residue R.sup.9 must
be present between the double bond and Y.sup.2, which carbon
residue R.sup.9 represents a linear or branched, optionally
substituted alkyl chain having a minimum length of 1 methylene
group, and wherein R.sup.6, R.sup.7 and R.sup.8 mutually
independently represent hydrogen or an optionally aryl- or
halosubstituted alkyl residue.
[0042] Any known free-radically polymerizable olefins and
substituted olefins may in principle be used in the free-radically
polymerizable, ethylenically unsaturated monomers A. Substituents
which may be considered are, for example, hydrogen (H), linear or
branched alkyl residues (R) having 1 to 20 carbon atoms, which may
optionally also have further substituents,
.alpha.,.beta.-unsaturated linear or branched alkenyl or alkynyl
residues, which may optionally also have further substituents,
cycloalkyl residues, which may also have heteroatoms, such as, O, N
or S in the ring and optionally further substituents, optionally
substituted aryl or heteroaryl residues, halogen, CN, CF.sub.3,
COOR, CONHR, CONR.sub.2, COR (where R=C.sub.1-C.sub.20).
[0043] The free-radically polymerizable double bond of the
ethylenically unsaturated monomers A may also be part of a ring
such as in cyclic olefins or olefinically unsaturated anhydrides or
imides.
[0044] Preferably used monomers for the production of Q comprise:
(meth)arylic acid esters of C.sub.1-C.sub.20 alcohols,
acrylonitrile, cyanoacrylic acid esters of C.sub.1-C.sub.20
alcohols, maleic acid diesters of C.sub.1-C.sub.6 alcohols, maleic
anhydride, vinylpyridines, vinyl(alkylpyrroles), vinyloxazoles,
vinyloxazolines, vinylthiazoles, vinylimidazoles, vinylpyrimidines,
vinyl ketones, styrene or styrene derivates, which have in .alpha.
(x position a C.sub.1-C.sub.6 alkyl residue or halogen and have up
to three further substituents on the aromatic ring. Butyl acrylate,
2-ethylhexyl arcylate, methyl methacrylate, butyl methacrylate,
cyclohexyl methacrylate, isobomyl methacrylate, maleic anhydride or
styrene are preferably used.
[0045] The initiator compound B comprises substances of the formula
R.sup.1R.sup.2R.sup.3X containing one or more free-radically
abstractable or transferable atoms or groups of atoms X, in which
R.sup.1 represents either X or a linear or branched
C.sub.1-c.sub.20 alkyl residue, which is substituted either with X
or with Y.sup.1 and optionally further residues and R.sup.2,
R.sup.3 mutually independently represent hydrogen or optionally
substituted, linear or branched C.sub.1-C.sub.20 aliphatic or
C.sub.6-c.sub.24 aromatic hydrocarbon residues or
electron-attracting substituents such as, for example, COOR, CN,
NO.sub.2, COCl, CONHR, CONR.sub.2 or COR (where
R=C.sub.1-C.sub.20). Compound B may either B1) contain a functional
group Y.sup.1 or B2) contain no Y.sup.1, but instead contain in the
substituents an additional group X (i.e., a total of two groups X
per initiator molecule).
[0046] In the initiator compounds B1, the residue R.sup.1 may be
described by the formula Y.sup.1--R.sup.10, in which R.sup.10
represents a linear or branched hydrocarbon residue with 1-10
carbon atoms and optionally substituted with aromatic residues,
which hydrocarbon residue may optionally also contain ether, ester,
amide, urethane or urea gropus and may additionally also contain
linear polymeric blocks such as polyether blocks, polyester blocks
or polyacrylate blocks, and Y.sup.1 represents a functional group
selected from --OH, --Cl, --COOH, --COOR, --CN, --NO.sub.2,
--SO.sub.3H, --COCl, --CONHR, --CONR.sub.2, --OR, --OP(.dbd.O)R,
--OP(.dbd.O)(OR), --OP(.dbd.O)(OR).sub.2 or --C(.dbd.O)R and R,
R.sup.1, R.sup.2 and R.sup.3 have the above-stated meaning.
[0047] Compounds of the formulae 2
[0048] are preferably used as component B1, wherein Hal=Cl or Br,
R.sup.13=C.sub.1-C.sub.6 alkyl, R.sup.14=H or CH.sub.3, n=1-10 and
m=1-225.
[0049] In initiator compounds B2 residue R.sup.1 may be identical
to X or be described by the formula X--CR.sup.10R.sup.11R.sup.12,
in which R.sup.2, R.sup.3 and R.sup.10 have the above-stated
meaning and R.sup.11 and R.sup.12 mutually independently represent
hydrogen or optionally substituted, linear or branched aliphatic or
aromatic hydrocarbon residues. Compounds of the formulae 3
[0050] are preferably used as component B2, wherein Hal=Cl or Br,
R.sup.13=C.sub.1-C.sub.6 alkyl, R.sup.14=HorCH.sub.3, n=1-225and
m=2-6.
[0051] The transition metal compound C comprises substances of the
formula M.sub.pZ.sub.q, which are prepared from a cation of a metal
M from the group comprising Cu, Fe, Ru, Cr, Mo, Wo, Mn, Rh, Re, Co,
Ni, V, Zn, Au, Ag or Sm, wherein M may be present in the transition
metal compound in different oxidation states and may participate in
a reversible redox process, and an anion Z from the group
comprising halide, hydroxide, C.sub.1-C.sub.6 alkoxy,
SO.sub.4.sup.2-, PO.sub.4.sup.3-, R.sup.4PO.sub.4.sup.2-,
R.sup.4R.sup.5PO.sub.4.sup.-, R.sup.3R.sup.4R.sup.5P--,
CF.sub.3COO--, PF.sub.6.sup.-, CH.sub.3SO.sub.3.sup.-, ArSO3.sup.-,
CN.sup.- oder R.sup.4COO.sup.-, wherein R.sup.4, R.sup.5 mutually
independently represent hydrogen or an optionally C.sub.6-C.sub.24
aryl- or halo-substituted (Cl. Br) alkyl residue, and wherein p and
q denote a number of 1, 2, 3, 4 or 5 and are not determined by the
valencies of M and Z in the transition metal compound. CuCl,
mixtures of CuCl and CuC1.sub.2, CuBr or mixtures of CuBr and
CuBr.sub.2 are preferably used as component C.
[0052] The anion Z of the transition metal compound is
conventionally the same as the abstractable group X of the
initiator. Z and X may, however, also be different.
[0053] Component D comprises one or more complex ligands L, which
may be mono- or polydentate, which contain one or more nitrogen,
oxygen, phosphorus or sulfur atoms and may combine with at least
one cation of the metal M to form complexes. Examples of such
ligands are diamines, diamides, aminoalcohols, diols,
hydroxycarboxylic acid esters, aminocarboxylic acid esters,
bipyridines, bipyrroles, phenanthrolines, cryptands, crown ethers
or porphyrins. Ligands which complex the central atom (for example
by means of 7r bonds), aromatic compounds, (poly)olefins or
(poly)alkynes, as well as cyclopentadienyl compounds may also be
suitable. Compounds of the formula 4
[0054] are, however, preferably used as component D, wherein
R.sup.15 to R.sup.18 mutually independently represent hydrogen or
C.sub.1-c.sub.20 aliphatic or C.sub.6-C.sub.24 aromatic hydrocarbon
residues, and R.sup.15 to R.sup.18 may optionally also be linked
together to form an unsaturated, optionally aromatic, ring
containing nitrogen, and wherein component D may also be attached
to a polymer or incorporated into a polymer chain by means of one
or more of residues R.sup.15 to R.sup.18.
[0055] It is essential to the invention that polymerization is
performed in the presence of a functionalizing reagent E. This
reagent comprises a compound of the formula
R.sup.6R.sup.7C.dbd.CR.sup.8(R.sup.9--Y.sup.2), which contains at
least one olefinic double bond and at least one functional group
Y.sup.2 reactive towards isocyanates, alcohols, carboxylic acids or
epoxides, wherein a carbon residue R.sup.9 must be present between
the double bond and Y.sup.2, which carbon residue R.sup.9
represents a linear or branched, optionally substituted
[0056] C.sub.1-C.sub.20 alkyl chain having a minimum length of 1
methylene group, and wherein R.sup.6, R.sup.7 and R.sup.8 mutually
independently represent hydrogen or an optionally aryl- or
halo-substituted alkyl residue. In some cases a mixture of such
compounds may also, but not preferably, be used. Component E is
preferably selected from compounds of the group. 5
[0057] wherein R.sup.19 represents hydrogen or a linear or branched
C.sub.1-C.sub.6 alkyl chain and R.sup.20 and R.sup.21 represent any
desired hydrocarbon residues having 1 to 20 C atoms, R.sup.22 is
hydrogen or a C.sub.1-C.sub.20 alkyl residue, preferably methyl, n
may be 1-4 and m my be 1-10. It is particularly preferred to use
2-propen-1-ol, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol or the
propoxylated derivates thereof obtained by addition of 1-10 mol of
propylene oxide onto the OH group.
[0058] In order to produce the desired telechelic substances using
the process according to the invention, components A to E must be
present in the system in certain molar ratios. The complex ligand D
should be present relative to the transition metal compound C at a
molar ratio of D:C of 1:1 to 4:1. preferably of .5:1 to 3.1. The
initiator compound B must here be present relative to the
transition metal compound C at a molar ratio of B:C of 0.3:1 to
5:1, preferably of 1:1 to 3:1. Component E is used in a quantity
corresponding to a molar ratio of B:C of 0.3:1 to 5:1, preferably
of 1:1 to 3:1. Component E is used in a quantity corresponding to a
molar ratio of C.dbd.C double bonds in component E to transferable
atoms/groups of atoms X in component B of at least 1:1, preferably
of at least 3:1.
[0059] The quantity of component A (monomers) to initiator compound
C is determined as a function of the desired molecular weight or
degree of polymerization of the telechelic substance. Since the
process according to the invention involves a living polymerization
reaction, from which termination or transfer reactions are
substantially absent, and component E does not undergo addition
onto the active chain ends until after component A has been
consumed, the person skilled in the art may readily calculate the
required initiator concentration [B] for a given initial monomer
concentration [A.sub.0] if a degree of polymerization P.sub.n is to
be achieved:
[B]=x.sub.p.multidot.[A.sub.0]/P.sub.n
[0060] wherein x.sub.p ([A.sub.0]-[A])/[A.sub.0] represents the
degree of concersion and [A] the actual monomer concentration at
conversion x.sub.p. It is evident from the above that telechelic
substances of any desired molecular weight may be produced using
the process according to the invention. Preferably, however,
molecular weights of 500<M.sub.n<10000, preferably of
100<M.sub.n<5000, are established. The molecular weight
distributions obtained are very narrow and are within the range
1.1<M.sub.w/M.sub.n<1.5.
[0061] The telechelic substances produed using the process
according to the invention have functionalities (Y.sup.1+Y.sup.2)
of 1.6 to 2.0, generally, however, of >1.8 to 2.0, but never of
>2.0. One of the two end groups may also be present in
derivatized or protected form, wherein functionalities of 0.8 to
1.0, geneerally of >0.9 to 1.0, are then obtained.
[0062] The reaction in the process according to the invention may
be perfomed at temperatures of between room temperature and
180.degree. C., preferably of between 80.degree. C. and 150.degree.
C., preferably of between 90.degree. C. and 130.degree. C. the
reaction may be performed both without solvents (in the monomer or
monomer mixture) and in an organic solvent known in lacquer
technology. It may be performed in air or under a protective gas
atmosphere; a protective gas atmosphere (for example nitrogen or
argon) is preferably used.
[0063] The telechelic substances Y.sup.1--Q--Y.sup.2 according to
the invention may be used as structural units in block copolymers,
which are present, for example, in plastics, fibers, adhesives or
binders or binder components in coating compositions. Depending
upon the chemical nature of the plastics, fibers, adhesives or
binders and the functionalities of the other structural units
present therein, the functional groups Y.sup.1, Y.sup.2 of the
telechelic substance may be selected such that the synthesis
reactions to yield the block copolymer proceed in a straightforward
and controlled manner. It is possible by means of the monomer
composition of the central block Q of the telechelic substance to
introduce properties into the block copolymers produced therefrom,
such as rigidity, flexibility, hydrophobicity, hydrophilicity,
deliberate incompatibilities or additional functionalities.
[0064] Depending upon the functionality Y.sup.1, Y.sup.2, the
telechelic substances according to the invention may also be used
in unmodified form as a binder, binder component, curing agent or
curing agent component in coating compositions and adhesives.
[0065] The invention is further illustrated but is not intended to
limited by the following examples in which all parts and
percentages are by weight unless otherwise specified.
EXAMPLES
Example 1
[0066] Production of a Telechelic Substance According to the
Invention
[0067] 1 equivalent (49 parts by weight) of CuCl, 3 equivalents
(234 parts by weight) of bipyridine, 18.8 equivalents (939 parts by
weight) of methyl methacrylate, 20 equivalents (582 parts by
weight) of allyl alcohol and 2 equivalents (246 parts by weight) of
4-hydroxybutyl-2-chloro-2-phenyl acetate was added to 710 parts by
weight of butyl acetate under a nitrogen atmosphere in a
multi-necked flask. The mixture was heated to 130.degree. C. and
stirred at this temperature for 60 hours. After this period, the
mixture was diluted with a quantity of dichloromethane
corresponding to the quantity of butyl acetate and this solution
was washed with a 5% hydrochloric acid solution. After phase
separation, the organic phase was evaporated under a vacuum and the
product precipitated by slowly running this solution into hexane.
After filtration and drying, a hydroxy-telechelic substance was
obtained at a yield of 91% which, according to GPC, had a number
average molecular weight of 1900 and a polydispersity of 1.25. The
degree of functionalization, determined by .sup.1H-NMR spectroscopy
and OH titration, was 1.8. In the MALDI-TOF spectrum,
bishydroxy-functional oligomers were detected as the principal
product, together with small quantities of monohydroxy-functional
oligomers; non-functional oligomers were not found.
Examples 2-6
[0068] The mixtures of the components started in table 1 (all
quantities stated as parts by weight) were combined and reacted and
made in (=isolation and purification of the crude product)
accordance with the procedure of Example 1:
1TABLE 1 Production of telechelic substances according to the
invention Example no. 1 2 3 4 5 6 CuCl 49 25 25 20 9 30 CuBr
Bipyridin 234 117 117 94 43 140 Methyl methacrylate 939 500 196 400
187 100 n-Butyl acrylate 894 128 2-Ethylhexyl acrylate 184 Allyl
alcohol 582 135 171 Allyl-N-(4-methyl- 175 112 153 344
phyenl)carbamate 4-Hydroxybutyl-2- 246 61 chloro-2-phenylacetate
N-(2-Hydroxyethyl)-2- 50 chloro-2-phenylacetamide 2-Bromoisobutyric
acid ethyl ester .alpha.,.alpha.-Dichlorotoluene 32 15 48 Butyl
acetate 710 440 440 440 180 440 Reaction time [h] 60 20 21 24 22 21
Reaction temp. [.degree. C.] 130 130 130 130 130 130 M.sub.n (GPC)
1900 6300 2500 3000 3100 2000 M.sub.w/M.sub.n (GPC) 1,25 1,14 1,39
1,43 1,25 1,43 Functionality* 1,8 1,9 1,97 1,95 >1.6 >1,8
*Explanations concerning end group functionality,
[0069] Examples 1-6:
[0070] Example 1: OH-functional initiator+end capping with allyl
alcohol
[0071] Examplex 2 and 3: OH-functional initiator+end capping ith
the penylurethane derivate of allyl alcohol
[0072] Example 4 and 6: double end capping with the phenylurethane
derivative of allyl alcohol.
[0073] Example 5: double end capping with allyl alcohol.
[0074] Although the invention has been described in detail in the
foregoing for the purpose of illustration, it is to be understood
that such detail is solely for that purpose and that variations can
be made therein by those skilled in tha art without departing from
the spirit and scope of the invention except as it may be limited
by the claims.
* * * * *