Polymer production

Details Polymer production Polymer production

2001-01-17

2003-05-06

Pezzuto, Helen L. (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S279000, C526S287000, C526S288000, C526S303100, C526S311000

Reexamination Certificate

active

06559261

ABSTRACT:

The present invention relates to methods of producing polymeric compounds, in particular using radiation curing such ultraviolet or thermal radiation, or chemical curing or electron beam initiated curing. Certain compounds which form polymers under the influence of u.v. light form a further aspect of the invention, as well as to polymers, coatings and adhesives obtained thereby.
The polymerisation of diallyamines using free radical initiation is known, for example from Solomon et al., J. Macromol. Sci.- Rev Macromol. Chem. c15 (1) 143-164 (1976). Free radical initiation of polymerisation requires quite extreme reaction conditions which can be generated only in production plants etc. It is not suitable for situations where in situ polymerisation is required.
Other cyclpolymerisation reactions are discussed by C. D. McLean et al., J. Macromol. Sci.-Chem., A10 (5), pp857-873 (1976). Yet further reactions are described in WO 97/16504, WO97/16472 where such reactions are used in a specialised way in the production of liquid crystal compounds.
The applicants have found that a broad range of compounds with at least two appropriately positioned multiple bonds and in particular double 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, beta or gamma to one or both of the double bonds to make them readily polymerisable under the influence of inter alia radiation. The term “readily polymerisable” means that the compounds will undergo polymerisation under moderate conditions of temperature and pressure (for example at room temperature and atmospheric pressure) in the presence of radiation and an initiator, in a period of less than 24 hours.
Polymeric compounds obtained therefrom include cyclic rings. These have many advantageous properties. In particular, the invention can be used to generate products such as adhesives (see copending British Patent application No 9816169.8), coatings, network polymers or conducting polymers (see copending British Patent Application No. 9816171.0) depending upon the other aspects of the structure of the starting materials.
In its broadest aspect, the invention provides a method for producing a polymeric material, said method comprising subjecting a starting material which includes two double bonds which are activated so that they will take part in a polymerisation reaction and wherein the double bonds are sufficiently close together to ensure that cyclopolymerisation will preferentially occur; to suitable conditions under which said polymerisation reaction will occur, provided that the starting material is other than triallyamine hydrochloride.
Specifically, the invention provides a method for producing a polymeric material, said method comprising subjecting a starting material which comprises a group of sub-formula (I)
where
R
1
is CR
a
where R
a
is hydrogen of alkyl, 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;
provided 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 which is able to activate a cyclopolymerisation reaction; to suitable conditions under which a cyclopolymerisation reaction will occur, subject to the following further provisos:
(i) that the starting material is other than triallyamine hydrochloride;
(ii) that when R
1
and R
6
together form the sole electron withdrawing group and R
1
is a group N
+
R
12
(Z
m−
)
1/m
, where R
12
is hydrogen or hydrocarbyl, Z is an anion of charge m and R
6
is a bond, said conditions are subjecting the compound to radiation in the substantial absence of a solvent or sulphur dioxide gas; and
(iii) that where R
1
and R
6
together form the sole electron withdrawing group and R
1
is CH and R
6
is OC(O), then the compound does not further contain a mesogenic group, or contains at least one further group of sub-formula (I).
As used herein, the expression “in the substantial absence of solvent” means that there is either no solvent present or there is insufficient solvent present to completely dissolve the reagents, although a small amount of a diluent may be present to allow the reagents to flow.
Conditions under which polymerisation will occur include the influence of radiation or an electron beam, or in the presence of a chemical initiator. Radiation or electron beam induced polymerisation is suitably effected in the substantial absence of a solvent.
In particular X
1
and Y
1
are groups CX
2
X
3
and CY
2
Y
3
respectively and the dotted lines represent an absence of a bond. Thus preferred compounds are those of sub-formula (IA)
where R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, X
2
, X
3
, Y
2
and Y
3
are as defined above. One or more such starting materials may be polymerised together. When more than one starting material is used, a copolymer will result.
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 there are no more than five atoms in between or linking the double bonds in the starting material so that when the cyclopolymerisation takes place, for example as illustrated hereinafter in FIG. 1, the size of the rings formed does not exceed 7. Preferably, there are from 3 to 5 atoms in between the double bonds.
Suitably the starting material is one which will cyclopolymerise in the sort of conditions used in polymer production. This may comprise the application of radiation such as uv or thermal radiation, where necessary in the presence of a photoinitiator, by the application of other sorts of initiator such as chemical initiators, or by initiation using an electron beam. The expression “chemical initiator” as used herein refers to compounds which can initiate polymerisation such as free radical initiators and ion initiators such as cationic or anionic initiators as are understood in the art.
Preferably, the starting materials polymerise under the influence of ultraviolet or thermal radiation, preferably ultraviolet radiation. Cyclopolymerisation may take place either spontaneously or in the presence of a suitable initiator. Examples of suitable initiators include 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 acet

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