Composition and process for controlled radical...

Details Composition and process for controlled radical... Composition and process for controlled radical...

1999-12-15

2003-06-03

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S083000, C526S084000, C526S346000, C526S329200, C526S344000, C526S348700, C526S352000, C526S351000, C526S348200, C526S348500, C526S348600, C526S335000, C526S310000, C526S319000

Reexamination Certificate

active

06573347

ABSTRACT:

The present invention relates to a polymerizable composition comprising a) at least one ethylenically unsaturated monomer and b1) at least one multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl and a free radical initiator or b2) at least one multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl-ether. Further aspects of the present invention are a process for polymerizing ethylenically unsaturated monomers, the (co)polymers obtainable by this process and the use of multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyls in combination with a free radical initiator, or a multifunctional triazinyl based 2,2,6,6 tetramethylpiperidine-1-oxyl-ethers for controlled polymerization.
In particular, this invention relates to stable free radical-mediated polymerization processes which provide homopolymers, random copolymers, block copolymers, multiblock copolymers, graft copolymers and the like, at enhanced rates of polymerization and enhanced monomer to polymer conversions.
U.S. Pat. No. 4,581,429 to Solomon et al., issued Apr. 8, 1986, discloses a free radical polymerization process which controls the growth of polymer chains to produce short chain or oligomeric homopolymers and copolymers, including block and graft copolymers. The process employs an initiator having the formula (in part) R′R″N—O—X, where X is a free radical species capable of polymerizing unsaturated monomers. The reactions typically have low conversion rates. Specifically mentioned radical R′R″N—O·groups are derived from 1,1,3,3 tetraethylisoindoline, 1,1,3,3 tetrapropylisoindoline, 2,2,6,6 tetramethylpiperidine, 2,2,5,5 tetramethylpyrrolidine or di-t-butylamine. However, the suggested compounds do not fulfill all requirements. Particularly the polymerization of acrylates does not proceed fast enough and/or the monomer to polymer conversion is not as high as desired.
EP-A-735 052 discloses a method for preparing thermoplastic polymers of narrow polydispersities by free radical-inibated polymerization, which comprises adding a free radical initiator and a stable free radical agent to the monomer compound. However the compounds specifically disclosed therein do not fully satisfy the need of high conversion rates, which is a prerequisite for industrial scale up.
JP 08-269117 published 31.3.1995 describes the polymerization of vinyl monomers with nitroxides such as the nitroxides of bis(2,2,6,6-tetramethyl-4-piperidyl)sebaic acid ester and tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4 butanetetracarboxylate.
It remains however still a problem to achieve a high conversion in short time at a low polydispersity.
The compounds of the present invention provide polymeric resin products having low polydispersity, particularly when the polymer is heated for a certain time after polymerization is completed. In addition the monomer to polymer conversion proceeds in a short time. Thus making the compounds particularly suitable for industrial polymerization processes.
One subject of the invention is a polymerizable composition, comprising
a) at least one ethylenically unsaturated monomer or oligomer, and
b) a compound of formula (I)
 in which n is the number 1 or 2, and R
1
is a group of the formula
 in which
G
1
and G
2
are hydrogen, methyl or, together, are a substituent ═O,
E is —O— or —ND
3
—,
A is C
2
-C
6
alkylene or —(CH
2
)
3
—O— and
x
1
is the number 0 or 1,
D
3
is hydrogen, C
1
-C
12
alkyl, C
2
-C
5
hydroxyalkyl or C
5
-C
7
cycloalkyl,
R
2
is identical to R
1
or is one of the groups —N(G
21
)(G
22
), —OG
23
, —N(H)(CH
2
OG
23
) or —N(CH
2
OG
23
)
2
,
R
3
, if n=1, is identical to R
1
and,
if n=2, is an —E—D
4
—E— group, in which D
4
is
C
2
-C
8
alkylene or C
2
-C
8
alkylene which is interrupted by 1 or 2 —NG
21
— groups,
G
21
is C
1
-C
12
alkyl, cyclohexyl, benzyl or C
1
-C
4
-hydroxyalkyl or a group of the formula
G
22
is C
1
-C
12
alkyl, cyclohexyl, benzyl or C
1
-C
4
hydroxyalkyl, and
G
23
is hydrogen, C
1
-C
12
alkyl or phenyl, or
G
21
and G
22
together are C
4
-C
5
alkylene or C
4
-C
5
oxaalkylene, for example —CH
2
CH
2
—O—
CH
2
CH
2
—, or a group of the formula —CH
2
CH
2
—N(G
11
)—CH
2
CH
2
—; and
G
11
is O· or —O—X, wherein
X represents a group such that the free radical X· derived from X is capable of initiating polymerization of ethylenically unsaturated monomers; and
if G
11
is O·, a source of free radicals is additionally present.
Some examples of the several variables in the formula (I) are given below.
Any C
1
-C
12
alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tertbutyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Any hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
Any C
5
-C
7
cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.
C
2
-C
6
alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
If G
21
and G
22
together are C
4
-C
5
alkylene or oxaalkylene, they are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
Preferably n is 1 in formula (I).
Particularly preferred compounds of formula (I) are, wherein n is 1, R
1
and R
3
are a group
and R
2
is identical to R
1
and R
3
or is a group —N(G
21
)(G
22
) and the other substituents are as defined above.
Most preferred compounds of formula (I) are, wherein n is 1;
R
1
and R
3
are a group of formula
R
2
is identical to R
1
and R
3
, or is a group —N(G
21
)(G
22
),
wherein x
1
is 0; G
1
is hydrogen; G
11
is O·; E is —ND
3
; D
3
is C
1
-C
12
alkyl and G
21
and G
22
are independently C
1
-C
12
alkyl.
Preferably X is selected from the group consisting of —CH(aryl)
2
, —CH
2
-aryl,
—CH
2
—CH
2
—aryl,
(C
5
-C
6
cycloalkyl)
2
CCN, CH
2
CH═CH
2
, (C
1
-C
12
)alkyl-CR
30
—C(O)—(C
1
-C
12
)alkyl, (C
1
-C
12
)alkyl-CR
30
—C(O)—(C
6
-C
10
)aryl, (C
1
-C
12
)alkyl-CR
30
—C(O)—(C
1
-C
12
)alkoxy, (C
1
-C
12
)alkyl-CR
30
—C(O)-phenoxy, (C
1
-C
12
)alkyl-CR
30
—C(O)—N-di(C
1
-C
12
)alkyl, (C
1
-C
12
)alkyl-CR
30
—CO—NH(C
1
-C
12
)alkyl, (C
1
-C
12
)alkyl-CR
30
—CO—NH
2
, —CH
2
CH═CH—CH
3
, —CH
2
—C(CH
3
)═CH
2
, —CH
2
—CH═CH-phenyl,
—O—C(O)—C
1
-C
12
alkyl, —O—C(O)—(C
6
-C
10
)aryl,
(C
1
-C
12
)alkyl-CR
30
—CN,
 wherein
R
30
is hydrogen or C
1
-C
12
alkyl;
the aryl groups are unsubstituted or substituted with C
1
-C
12
alkyl, halogen, C
1
-C
12
alkoxy, C
1
-C
12
alkylcarbonyl, glycidyloxy, OH, —COOH or —COOC
1
-C
12
alkyl.
Aryl is phenyl or naphthyl.
More preferably X is selected from the group consisting of —CH
2
-phenyl, CH
3
CH-phenyl, (CH
3
)
2
C-phenyl, (CH
3
)
2
CCN, —H
2
CH═CH
2
, and CH
3
CH═CH═CH
2
.
Most preferred is a compound of formula (1), wherein G
11
is —O·.
Examples of groups of polyalkylpiperidine compounds according to formula (I) are the compounds of the following formulae:
where R′ has the same meaning as in compound 76.
In the above formulae G
11
represents —O·, or —O—X, wherein X is as defined above.
Preferably the compound of formula (I) is present in an amount of from 0.01 mol-% to 30 mol-%, based on the monomer or monomer mixture, more preferably in an amount of from 0.05 mol-% to 20 mol-%, and most preferably in an amount of from 0.1 mol-% to 10 mol-% based on the monomer or monomer mixture.
The compounds according to formula (I) are in principal known and may be prepared according to standard procedures as for example described in U.S. Pat. No. 5,216,156, U.S. Pat. Nos. 5,004,770 or 5,204,473.
Preferably the source of a free radical initiator is a bis-azo compound, a peroxide or a hydroperoxide.
More preferably, the source of free radicals is 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methyl-butyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyr

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