Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1998-04-10
2001-07-17
Lipman, Bernard (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S318400
Reexamination Certificate
active
06262204
ABSTRACT:
TABLE OF CONTENTS
1. Background of the Invention
1.1. Technical Field
1.2. Description of Related Art
2. Summary of the Invention
3. Description of the Preferred Embodiments
3.1. Example 1 (a-n)
3.2. Example 2
3.3. Example 3 to 5
3.4. Examples 6, 7, and 8
3.5. Examples 9 and 10
4. claims
5. Abstract of the Disclosure
1. BACKGROUND OF THE PRESENT INVENTION
1.1. Technical Field
The present invention relates to an initiation system for anionic polymerization of (meth)acrylic monomers and, possibly, ethylenically unsaturated monomers that can be copolymerized with these (meth)acrylic monomers to obtain homopolymers, block or random copolymers and star copolymers comprising arms formed of at least one (meth)acrylic sequence bonded to a core or node formed of a multifunctional compound (for example, a deactivating agent or a monomer lead to a polymer, whether or not cross-linked).
Anionic polymerization of (meth)acrylic monomers is difficult to control as a result of secondary reactions between the monomer and the initiator and/or the ends of growing anionic chains or due to termination and chain transfer reactions.
However, anionic polymerization is of interest in the sense that if it is conducted carefully under controlled conditions, polymers with a well-defined structure result.
1.2. Description of Related Art
Research has been undertaken for better control of (meth)acrylic monomer polymerization and to thus avoid secondary reactions.
Thus, in European Patent Application EP-A-524054, the anionic polymerization of (meth)acrylic polymers in the presence of an initiation system comprising a monofunctional or difunctional initiator and a ligand formed by an alkoxy alcoholate of an alkaline metal is described. With this process, polymerization is well controlled, especially at low temperatures.
An initiation system permitting well-controlled anionic polymerization, which can be used under conditions easy to create in industry and is less costly and, particularly, usable at temperatures closer to ambient temperature, is still being sought.
2. SUMMARY OF THE INVENTION
The present invention relates to an initiation system comprising at least one initiator, with the exception of amides of alkaline metals, and at least one alkaline metal alcoholate of the formula ROM, in which M is an alkaline metal and R represents a group
Q—R
1
—(OR
2
—)
m
wherein Q is a heterocyclic compound with 5 or 6 chain links, substituted or not, having 1 or 2 oxygen atoms as heteroatoms, R
1
and R
2
represent an alkylene group, linear or branched at C
1
-C
4
, and m is equal to 0, 1, 2 or 3.
The present invention also relates to the application of the initiation system to the preparation of (meth)acrylic (co)polymers and, possibly, ethylenically unsaturated monomers that can be copolymerized with (meth)acrylic monomers.
3. DESCRIPTION OF THE PREFERRED EMBODIMENTS
The inventive initiation system for polymerization of (meth)acrylic monomers and possibly ethylenically unsaturated monomers, which can be polymerized with these (meth)acrylic monomers, is composed of at least one initiator, with the exception of alkaline metal amides, and at least one alcoholate of the formula
ROM (I)
wherein
M represents an alkaline metal,
R represents a group
Q—R
1
—(OR
2
—)
m
wherein:
Q represents a heterocyclic compound with 5 or 6 chain links comprising 1 or 2 oxygen atoms as the only heteroatom(s), whether or not substituted with an alkyl group with 1 to 8 carbon atoms, a cycloalkyl at C
5
-C
8
or substituted by/or condensed to a heterocyclic compound with 5 to 8 chain links comprising 1 or 2 heteroatoms;
R
1
and R
2
, identical or different, each representing an alkylene group at C
1
-C
4
, linear or branched, with R
1
being bonded to heterocyclic compound Q at &agr; of an oxygen atom,
m is equal to 0, 1, 2 or 3.
In Formula I of the ligand, group Q is preferably a hydrogenated heterocyclic compound and, in particular, can represent a tetrahydrofuranyl-2-, 5-methyltetrahydrofuranyl-2-,tetrahydropyranyl-2-,1,3-dioxolanyl-2-,1,3-dioxolanyl5-, 1,3-dioxanyl-2-, 1,3-dioxanyl-6-, 1,4-dioxanyl-2-, 1,4-dioxoaspiro [4,5]decan-2-yl-, 1,7-dioxaspiro[5,5]undecan-2-yl, or 1,5,7,11-tetraoxaspiro[5,5]-undecan-2-yl group.
R
1
may, for example, be a methylene, ethylene, propylene, butylene, or isopropylene group, preferably methylene.
R
2
may represent, for example, a methylene, ethylene, propylene, butylene, or isopropylene group, preferably ethylene.
m is advantageously equal to 0, 1 or 2.
M preferably represents lithium.
Q may be substituted by or condensed to a heterocyclic compound containing 1 or 2 identical or different heteroatoms, such as oxygen, nitrogen or sulfur.
A particularly useful ligand is lithium tetrahydrofuranyl-2-methoxylate or -2-ethoxylate.
The initiator in the initiation system pursuant to the invention may be any mono- or di-functional initiator for anionic polymerization.
The monofunctional initiator may be selected, in particular, from among compounds of the formula:
(R′)
p
—M′ (II)
wherein
M′ represents an alkaline metal or an alkaline earth (valence p of 1 or 2); and
R′ designates an alkyl radical with straight or branched chain, containing 2 to 8 carbon atoms, or an aryl radical with one or more cycles, possibly substituted, or an alkenyl radical at C
2
-C
6
substituted by an aryl or alkylaryl group, or a linear or branched alkyl radical containing 1 to 8 carbon atoms, substituted by at least one phenyl group or an alkylaryl radical, in which the alkyl group has 1 to 8 carbon atoms.
Such monofunctional initiators are, for example, sec.-butyllithium, n-butyllithium, fluorenyllithium, alpha-methylstyryllithium, 1,1-diphenylhexyl lithium, diphenylmethyllithium or -sodium or -potassium, and 1,1-diphenyl-3-methylpentyllithium.
The monofunctional initiator can also be &agr;-lithioisobutyrates.
The difunctional initiators can be of Formula (III)
wherein:
M′
1
is an alkaline metal; and
R
11
represents an bivalent organic radical, whether aliphatic, cycloaliphatic, aromatic or containing at least one cycloaliphatic or aromatic group, R
11
may contain substituents; and
R
12
and R
13
each independently represent a monovalent organic radical, whether aliphatic, cycloaliphatic, aromatic or containing at least one cycloaliphatic or aromatic group, R
12
and R
13
may contain substituents.
The difunctional initiator may be selected, in particular, from among compounds such as 1,1,4,4-tetraphenyl-1,4-dilithio-butane and 1,1,4,4-tetraphenyl-1,4-disodiobutane.
One may also use difunctional initiators such as initiator precursors, e.g., lithium naphthalene, sodium naphthalene, potassium naphthalene or homologues thereof. The reaction product from two organomonolithiated initiator equivalents (such as ter.-butyllithium) with 1,3-diisopropenylbenzene can also be used.
The initiator may also be a silylated compound. Monofunctional, it may correspond to the following formula:
wherein:
R
3
, R
4
, R
5
each independently represent a linear or branched alkyl radical containing 1 to 8 carbon atoms;
R
6
represents a linear or branched alkylene radical containing 1 to 8 carbon atoms;
M″ designates an alkaline metal or alkaline earth metal (valence q or 1 or 2).
The silylated initiator may also be difunctional, and is then selected in particular from among compounds of Formula (V):
wherein:
R
7
and R
8
each independently represent a linear or branched alkyl radical containing 1 to 8 carbon atoms;
R
9
and R
10
each independently represent a linear or branched alkylene radical containing 1 to 8 carbon atoms; and
M′″ designates an alkaline metal.
In Formulae (IV) or (V) above, it is preferable for R
3
, R
4
, R
5
, R
7
and R
8
to each independently represent an alkyl radical with 1 to 4 carbon atoms, quite particularly methyl, and for R
6
, R
9
and R
10
to each independently represent an alkylene radical with 1 or 2 carbon atoms, in particular the methylene radical, and for M″ and M′″ to each represent lith
Maurer Andreas R.
Muller Axel H. E.
Navarro Christophe
Atofina
Lipman Bernard
Pennie & Edmonds LLP
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