Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2001-02-15
2003-06-10
Berman, Susan W. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S171000, C522S168000, C522S173000, C522S180000, C522S182000, C522S186000, C522S188000, C526S256000, C526S258000, C526S263000, C526S274000, C526S286000, C526S310000, C526S328000, C526S328500, C526S346000, C526S347000, C526S348000, C526S348800, C564S281000, C564S291000, C564S292000, C564S296000, C568S008000, C568S013000, C568S017000, C568S018000, C568S074000, C568S075000, C568S077000
Reexamination Certificate
active
06576684
ABSTRACT:
The present invention relates to compositions, from which radically initiated oligomers/polymers having a controlled molecular weight, low polydispersity and a vinyl or dienyl end group can be prepared. Further subjects of the invention are a process for controlled radical polymerization, oligomers/polymers obtainable by said process and the use of specific addition fragmentation agents for the polymerization process. The addition fragmentation agents are new in part and these are also subject of the present invention.
Polymers of limited molecular weight, or oligomers, are useful as precursors in the manufacture of other polymeric materials and as additives in plastics, elastomers and surface coating compositions, as well as being useful in their own right in many applications.
In conventional polymerization practice, the manufacture of oligomers requires the use of an initiator which acts as free radical source and of a chain transfer agent. The chain transfer agent controls the molecular weight of the polymer molecule by reacting with the propagating polymer chain. At least a part of the transfer agent is incorporated into the polymer and thus is consumed during the process. The incorporated residue of the chain transfer agent can lead to undesirable end-groups on the polymer. Common chain transfer agents are for example alkanethiols, which cause an objectionable odour.
To avoid these deficiencies WO 88/04304 suggests nonionic acrylate or styrene derivatives as chain transfer agents for controlled radical polymerization.
The use of addition fragmentation agents to control molecular weight is known and a variety of compounds have already been suggested as for example described by Colombani et al. in “Addition Fragmentation Processes in Free Radical Polymerization”, Prog. Polym. Sci., Vol. 21, 439-503, 1996. However there is still a need to provide easily accessible compounds which are highly efficient in thermally and in photochemically induced radical polymerization.
Y. Yagci et al. in J. Polym. Sci., Part A, Polym. Chem. Vol. 34, 3621-3624 (1996) disclose the use of allyl onium salts, in particular pyridinium salts, together with radical initiators for cationic polymerization.
Surprisingly it has been found that specific allyl or dienyl cationic systems are highly efficient addition fragmentation agents, useful for the control of molecular weight build up of radical polymerizations. The chain transfer coefficient c
x
is in many cases close to the theoretically ideal value of 1. Polydispersity of the oligomers/polymers is generally small and in many cases below 2. The compounds are easily accessible thus being ideally suitable for industrial applications.
These polymerization processes will also control the physical properties of the resulting polymers such as viscosity, hardness, gel content, processability, clarity, high gloss, durability, and the like.
The polymerization processes and resin products of the present invention are useful in many applications, including a variety of specialty applications, such as for the preparation of block copolymers which are useful as compatibilizing agents for polymer blends, or dispersing agents for coating systems or for the preparation of narrow molecular weight resins or oligomers for use in coating technologies and thermoplastic films or as toner resins and liquid immersion development ink resins or ink additives used for electrophotographic imaging processes.
One object of the present invention is a composition comprising
a) at least one ethylenically unsaturated monomer or oligomer
b) at least one radical initiator which forms a radical upon heating or upon irradiation with (UV) light from 305 nm to 450 nm and
c) a compound of formula (Ia), (Ib) or (Ic)
Y is a group which activates the double bond towards Michael addition;
X is halogen or the anion of a mono carboxylic acid from 1-12 carbon atoms, a monovalent oxo acid or complex acid;
n is 0 or 1;
R
1
, R
2
, R
3
are independently of each other hydrogen, unsubstituted C
1
-C
18
alkyl, C
3
-C
18
alkyl, interrupted by at least one nitrogen or oxygen atom, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, C
7
-C
9
phenylalkyl, C
3
-C
12
cycloalkyl or C
3
-C
12
cycloalkyl containing at least one nitrogen or oxygen atom; or
C
1
-C
18
alkyl or C
3
-C
18
alkyl interrupted by at least one nitrogen or oxygen atom, C
3
-C
18
alkenyl, C
3
-C
18
alkynyl, C
7
-C
9
phenylalkyl, C
3
-C
12
cycloalkyl or C
3
-C
12
cycloalkyl containing at least one nitrogen or oxygen atom, which are substituted by NO
2
, halogen, amino, hydroxy, cyano, carboxy, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, C
1
-C
4
alkylamino, di(C
1
-C
4
alkyl)amino or by a group —O—C(O)—C
1
-C
18
alkyl; or
phenyl, naphthyl, which are unsubstituted or substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, halogen, cyano, hydroxy, carboxy, C
1
-C
4
alkylamino or di(C
1
-C
4
alkyl)amino; or
R
1
and R
2
, together with the linking hetero atom, form a C
3
-C
12
heterocycloalkyl radical; or
R
1
and R
2
form a group,
or
R
1
, R
2
and R
3
form a group
Halogen is fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.
The alkyl radicals in the various substituents may be linear or branched. Examples of alkyl containing 1 to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Alkenyl with 3 to 18 carbon atoms is a linear or branched radical as for example propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n-2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl oder n-4-octadecenyl. Preferred is alkenyl with 3 bis 12, particularly preferred with 3 to 6 carbon atoms.
Alkinyl with 3 to 18 is a linear or branched radical as for example propinyl (—CH
2
—C≡CH), 2-butinyl, 3-butinyl, n-2-octinyl, oder n-2-octadecinyl. Preferred is alkinyl with 3 to 12, particularly preferred with 3 to 6 carbon atoms.
C
3
-C
12
cycloalkyl is typically, cyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl.
Cycloalkyl which is interrupted by at least one O or N atom is for example 2-tetrahydropyran-yl, tetrahydrofurane-yl, 1,4 dioxan-yl, pyrrolidin-yl, tetrahydrothiophen-yl, pyrazolidin-yl, imidazolidin-yl, butyrolactone-yl, caprolactame-yl.
C
7
-C
9
phenylalkyl is for example benzyl, phenylethyl or phenylpropyl.
C
3
-C
18
alkyl interrupted by at least one O atom is for example —CH
2
—CH
2
—O—CH
2
—CH
3
, —CH
2
—CH
2
—O—CH
3
or —CH
2
—CH
2
—O—CH
2
—CH
2
—CH
2
—O—CH
2
—CH
3
. It is preferably derived from polyethlene glycol. A general description is —((CH
2
)
a
—O)
b
—H/CH
3
, wherein a is a number from 1 to 6 and b is a number from 2 to 10.
Y may be any substituent which facilitates Michael addition at the double bond. Preferably Y is CN, C(O)halogen, COOR
4
, C(O)R
4
, CONR
5
R
6
, phenyl or naphthyl which are unsubstituted or substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, halogen, nitro, cyano, hydroxy, carboxy, C
1
-C
4
alkylamino or di(C
1
-C
4
alkyl)amino; and R
4
, R
5
and R
6
are hydrogen or C
1
-C
18
alkyl.
More preferably Y is CN, COOR
4
or phenyl which is unsubstituted or substituted by C
1
-C
4
alkyl, C
1
-C
4
alkoxy, C
1
-C
4
alkylthio, halogen, cyano, hydroxy, carboxy, C
1
-C
4
alkylamino or di(C
1
-C
4
alkyl)amino; and R
4
is C
1
-C
4
alkyl.
Most preferably Y is CN, COOCH
3
, COOC
2
H
5
or phenyl.
X is halogen or the anion of a mono carboxylic acid from 1-12 carbon atoms, a monovalent oxo acid or complex acid.
Examples of monocarboxylic acids with 1 to 12 carbon atoms are formic acid, acetic acid, propionic acid, phenyl acetic acid, cyclohexane carbonic acid, mono-, di- and trichlor-acetic acid or mono-, di- and trifluor-acetic acid. Other suitable acids are benzoic acid, chlorbenzoic acid, methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, chlorbenzenesulfonic acid, trifluormethanesul
Desobry Vincent
Murer Peter
Schuwey Anne
Berman Susan W.
Ciba Specialty Chemicals Corporation
Stevenson Tyler A.
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