Diallylamine monomers and network polymers obtained therefrom

Details Diallylamine monomers and network polymers obtained therefrom Diallylamine monomers and network polymers obtained therefrom

2001-01-17

2003-08-19

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...

C522S173000, C522S178000, C522S182000, C522S181000, C522S180000, C526S239000, C526S274000, C526S277000, C526S278000, C526S286000, C526S288000, C526S298000, C526S310000, C526S312000, C568S001000, C568S003000, C568S008000, C568S010000, C568S014000, C568S027000, C568S028000, C564S082000, C564S463000, C564S505000, C564S509000, C560S025000, C560S048000

Reexamination Certificate

active

06608120

ABSTRACT:

The present invention relates to monomers which are useful in the production of polymers, and in particular to network polymers, to the polymers obtained therefrom and to methods of producing these polymers, in particular using radiation curing, for example ultraviolet or thermal radiation.
Many polymers such as polyethylenes, polystyrenes, polyvinylidene fluorides, polytetrafluoroethylenes (e.g. teflon™), nylons, polyesters etc. are used every day in a wide variety of purposes from plastic wrap and plastic cups to sensors and non-stick surfaces to yield high strength materials.
WO 98/29107 describes certain polydiallyamine-based bile acid sequestrants, which are formed by polymerisation of the monomer in solution.
The applicants have found that certain compounds with two or more multiple bonds may be activated by the presence of an electron withdrawing group, in particular where the electron withdrawing group is at a position which is alpha or beta to one or both of the double bonds to make them polymerisable, for example under the influence of radiation or an electron beam, or in the presence of a chemical initiator. Polymeric compounds obtained therefrom include cyclic rings. These have many advantageous properties. In particular, the invention can be used to generate products such as network polymers or conducting polymers depending upon the other aspects of the structure of the compounds.
Certain monomers are new and these form a further aspect of the invention. In particular, the invention provides a compound of formula (I)
where R
1
is CH and R
6
is a bond, or R
1
and R
6
together form an electron withdrawing group;
R
2
and R
3
are independently selected from (CR
7
R
8
)
n
, or a group CR
9
R
10
, —(CR
7
R
8
CR
9
R
10
)— or —(CR
9
R
10
CR
7
R
8
)— where n is 0, 1, or 2, R
7
and R
8
are independently selected from hydrogen or alkyl, and either one of R
9
or R
10
is hydrogen and the other is an electron withdrawing group, or R
9
and R
10
together form an electron withdrawing group, and
R
4
and R
5
are independently selected from CH or CR
11
where R
11
is an electron withdrawing group;
the dotted lines indicate the presence or absence of a bond, and X
1
is a group CX
2
X
3
where the dotted line bond to which it is attached is absent and a group CX
2
where the dotted line bond to which it is attached is present, Y
1
is a group CY
2
Y
3
where the dotted line bond to which it is attached is absent and a group CY
2
where the dotted line bond to which it is attached is present, and X
2
, X
3
, Y
2
and Y
3
are independently selected from hydrogen and fluorine;
R
16
is a bridging group of valency r and r is an integer of 2 or more, subject to the following provisos:
(i) that at least one of (a) R
1
and R
6
or (b) R
2
and R
3
or (c) R
4
and R
5
includes an electron withdrawing group.
Preferably the compounds of formula (I) are of formula (IA)
where R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
16
, X
2
, X
3
, Y
2
and Y
3
are as defined in relation to formula (I).
Suitably the compounds of formula (IA) are subject to the further proviso:
(ii) that where R
16
is a group —(CH
2
)
10
—, R
2
and R
3
are CH
2
groups, R
4
and R
5
are CH groups and X
1
, X
2
, X
3
and X
4
hydrogen, R
1
is other than a group N
+
CH
3
Br
−
where R
6
is a bond.
Suitably, where R
16
is a alkylene group, R
2
and R
3
are CH
2
groups, R
4
and R
5
are CH groups, X
1
, X
2
, X
3
and X
4
hydrogen, R
1
is other than a group N
+
R
12
(Z
m−
)
1/m
as hereinafter defined, where R
6
is a bond.
Preferably, where R
2
and R
3
are both (CR
7
R
8
)
n
, at least one n is 1 or 2. Suitably in formula (I), n is 1 or 2.
On polymerisation of these compounds, networks are formed whose properties may be selected depending upon the precise nature of the R
16
group, the amount of diluent, plasticiser or chain terminator present and the polymerisation conditions employed. Polymerisation will occur in accordance with the general scheme set out in
FIG. 1
hereinafter.
When the dotted bonds in sub formula (I) are present, the resulting polymer will comprise polyacetylene chains. This can lead to a conjugated system and consequently a conducting polymer.
Suitably the compound is designed such that it cyclopolymerises under the influence of ultraviolet or thermal radiation, preferably. ultraviolet radiation. Cyclopolymerisation may take place either spontaneously in the presence of the appropriate radiation or in the presence of a suitable initiator, for example 2,2′-azobisisobutyronitrile (AIBN), aromatic ketones such as benzophenones in particular acetophenone; chlorinated acetophenones such as di- or tri-chloroacetophenone; dialkoxyacetophenones such as dimethoxyacetophenones (sold under the Trade name “Irgacure 651”); dialkylhydroxyacetophenones such as dimethylhydroxyacetophenone (sold under the Trade name “Darocure 1173”); substituted dialkylhydroxyacetophenone alkyl ethers such compounds of formula
where R
y
is alkyl and in particular 2,2-dimethylethyl, R
x
is hydroxy or halogen such as chloro, and R
p
and R
q
are independently selected from alkyl or halogen such as chloro (examples of which are sold under the Trade names “Darocure 1116” and “Trigonal P1”); 1-benzoylcyclohexanol-2 (sold under the Trade name “Irgacure 184”); benzoin or derivatives such as benzoin acetate, benzoin alkyl ethers in particular benzoin butyl ether, dialkoxybenzoins such as dimethoxybenzoin or deoxybenzoin; dibenzyl ketone; acyloxime esters such as methyl or ethyl esters of acyloxime (sold under the trade name “Quantaqure PDO”); acylphosphine oxides, acylphosphonates such as dialkylacylphosphonate, ketosulphides for example of formula
where R
z
is alkyl and Ar is an aryl group; dibenzoyl disulphides such as 4,4′-dialkylbenzoyldisulphide; diphenyldithiocarbonate; benzophenone; 4,4′-bis(N,N-dialkylamino)benzophenone; fluorenone; thioxanthone; benzil; or a compound of formula
where Ar is an aryl group such as phenyl and R
z
is alkyl such as methyl (sold under the trade name “Speedcure BMDS”). The compound may be polymerised under the influence of a free radical or ion initiator as is understood in the art, as well as by application of an electron beam.
As used herein, the term “alkyl” refers to straight or branched chain alkyl groups, suitably containing up, to 20 and preferably up to 6 carbon atoms. The terms “alkenyl” and “alkynyl” refer to unsaturated straight of branched chains which include for example from 2-20 carbon atoms, for example from 2 to 6 carbon atoms. Chains may include one or more double or triple bonds respectively. In addition, the term “aryl” refers to aromatic groups such as phenyl or naphthyl.
The term “hydrocarbyl” refers to any structure comprising carbon and hydrogen atoms. For example, these may be alkyl, alkenyl, alkynyl, aryl such as phenyl or napthyl, aralkyl, cycloalkyl, cycloalkenyl or cycloalkynyl. Suitably they will contain up to 20 and preferably up to 10 carbon atoms. The term “heterocyclyl” includes aromatic or non-aromatic rings, for example containing from 4 to 20, suitably from 5 to 10 ring atoms, at least one of which is a heteroatom such as oxygen, sulphur or nitrogen. Examples of such groups include furyl, thienyl, pyrrolyl, pyrrolidinyl, imidazolyl, triazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, iosquinolinyl, quinoxalinyl, benzthiazolyl, benzoxazolyl, benzothienyl or benzofuryl.
The term “functional group” refers to reactive groups such as halo, cyano, nitro, oxo, C(O)
n
R
a
, OR
a
, S(O)
t
R
a
, NR
b
R
c
, OC(O)NR
b
R
c
, C(O)NR
b
R
c
, OC(O)NR
b
R
c
, —NR
7
C(CO)
n
R
6
, —NR
a
CONR
b
R
c
, —C═NOR
a
, —N═CR
b
R
c
, S(O)
t
NR
b
R
c
, C(S)
n
R
a
, C(S)OR
a
, C(S)NR
b
R
c
or —NR
b
S(O)
t
R
a
where R
a
, R
b
and R
c
are independently selected from hydrogen or optionally substituted hydrocarbyl, or R
b
and R
c
together form an optionally substituted ring which optionally contains further heteroatoms such as S(O)
s

Affiliated with

Also associated with

Rating

Diallylamine monomers and network polymers obtained therefrom does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Diallylamine monomers and network polymers obtained therefrom, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Diallylamine monomers and network polymers obtained therefrom will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3116678