Polymerisable monomers and polymers

Details Polymerisable monomers and polymers Polymerisable monomers and polymers

1998-12-10

2002-02-05

Lipman, Bernard (Department: 1713)

Organic compounds -- part of the class 532-570 series

Organic compounds

Unsubstituted hydrocarbyl chain between the ring and the -c-...

C549S010000, C549S011000, C549S020000

Reexamination Certificate

active

06344556

ABSTRACT:

The invention relates to new unsaturated cyclic organic compounds which can be used as monomers or co-monomers in free radical polymerisation and polymers or co-polymers derived from these compounds. These compounds have the ability to ring open during polymerisation and provide examples of allylic monomers that will readily polymerise to high molecular weight polymers.
Monomers capable of ring opening (hereinafter referred to as “ring-opening monomers”) are important in minimising volume shrinkage during polymerisation. Additionally, ring-opening monomers are useful in providing an alternative method of incorporating functionalities such as amide, ester or carbonate into the backbone of a polymer. Generally, such functionalities are introduced by step growth (i.e. poly esterification) polymerisation rather than chain growth (i.e. free radical and ionic) polymerisation. The limitations of step growth polymerisation are that (a) very high conversion is required for high molecular weight polymers and (b) elimination products, such as, water or HCl are formed and require removal. In contrast, chain growth polymerisation results in very high molecular weight polymers from the beginning of the polymerisation.
There are many types of ring-opening monomers available for ionic polymerisation. However, there are only a limited number of ring-opening monomers available for free radical polymerisation. A review by Endo et al. in Chapter Five of
New Methods for Polymer Synthesis,
Plenum Press, New York, 1992 summarises the present state of the art. The major types of free radical polymerisation ring-opening monomers are vinyl cyclopropanes, cyclic vinyl ethers, cyclic ketene acetals (U.S. Pat. No. 4,857,620) spiro ortho esters and Spiro ortho carbonates.
Many of these known ring-opening monomers suffer from limitations. Ring opening of the vinyl cyclopropanes is a reversible process and substituents that favour ring opening may also inhibit polymer growth by excessive stabilisation of the ring-opened propagating radical. The oxygenated ring-opening monomers can also exhibit sensitivity to trace amounts of acid. This results in difficulties with their synthesis and subsequent storage. Furthermore, ring opening is not guaranteed and the final polymers can contain various proportions of opened and unopened rings. In addition, the Spiro ortho esters and spiro ortho carbonates have the following problems as described in
Expanding Monomers,
Eds. Sadhir, R. K. and Luck, R. M., CRC Press, Boca Raton,1992:
(i) They are sensitive to impurities. Impurities can prevent ring opening from occurring and make the polymerisation somewhat irreproducible.
ii) They have a low reactivity towards free radical polymerisation. This is partly due to side reactions, such as degradative chain transfer, in the polymerisation of allylic monomers.
iii) They have a low reactivity ratio with common commercial vinyl monomers, such as, styrene, methyl methacrylate and other monomers having a similar reactivity.
iv) They are crystalline compounds with low solubilities in organic solvents and monomers.
International Patent Application No. PCT/AU93/00667 discloses new cyclic acrylate monomers which undergo facile ring opening. These compounds are readily co-polymerised with monomers that co-polymerise with acrylates or styrenic monomers.
Some compounds within the scope of the present invention have been previously reported in the following references:
(1) Butler, J.; Kellogg, R. M.; van Bolhuis, F., “Functionalized Thia-crown Ethers. Synthesis, Structure and Properties.”,
J Chem Soc., Chem Comm.,
1990, 282;
(2) Tostikov, G. A.; Kanzafarov.F,Ya.; Kanzafarova, S. G.; Singizova, V. Kh., “Nucleophilic Thialation of Allyl Halides in the Presence of Phase-Transfer Catalysts”.,
Z. Org. Khim,
1986, 22(7), 1400;
(3) Martinetz, D.; Hiller, A. “Phase Transfer-Catalytic Conversion of Unsaturated Organic Halogen Compounds with Sodium Sulfide Nonahydrate.”,
Z. Chem.,
1978, 18(2), 61;
(4) Dietrich, E-M.; Schulze, K.; Muhlstadt, M., “1,5-Dithiacyclanes”, East German Patent No. 100 001., Sep. 5, 1973; and
(5) Richter, H.; Schulze, K; Muehlstaedt, M., “Reactions of 1,3-Dichloro-2-methylenepropane”,
Z Chem.,
1968, 8(6), 220.
References (1) to (5) are sparse in detail other than stating that the compound was made, together with a brief description of its synthesis. The use of these monocyclic monomers in free radical polymerisation is not disclosed in these references.
We have now found new unsaturated cyclic organic compounds which are capable of undergoing free radical polymerisation. These compounds include monocyclic compounds and bicyclic compounds in which two monocyclic units are tethered together.
Allylic monomers, such as allyl acetate, generally polymerise slowly, with a low degree of conversion and low molecular weight oligomers being formed. This is largely due to the occurrence of extensive degradative chain transfer during the polymerisation.
Some of the monocyclic compounds have been previously made and reported as discussed above, but their use in free radical polymerisation has not previously been disclosed. The cyclic compounds of the present invention avoid the degradative chain transfer problems of allylic monomers by converting the initially highly reactive, non-selective carbon-centered radical into a less reactive, more selective sulfur-centered radical by rapid ring-opening.
The bicyclic compounds are new and the use of such compounds is in the replacement of conventional bi-functional monomers, such as, CR 39 and dimethacrylates. Thus, crosslinked polymers may be produced with significantly less shrinkage. According to one aspect of the present invention there is provided compounds of the formulae:
wherein:
R
1
to R
4
may be the same or different and are selected from hydrogen, halogen, optionally substituted alkyl, optionally substituted aryl, nitrile, hydroxy, alkoxy, acyloxy and ester; or
R
1
and R
2
or R
3
and R
4
together form methylene;
X is selected from sulfur, sulfoxide, sulfone and disulfide;
Y is selected from sulfur, oxygen SO
2
, N—H, N-alkyl, N-aryl, acyl and CR
5
R
6
wherein R
5
and
R
6
are the same as R
1
to R
4
; and
Z
1
and Z
2
are linking functionalities.
The compounds of Formula
1
a
wherein R
1
to R
4
are hydrogen, X and Y are sulfur and
Z
1
is —(CH
2
)
2
— or —CH
2
—C(═CH
2
)—CH
2
— are known per se and therefore excluded from the compounds of the present invention.
Preferably X is S or SO
2
and Y is C(R
5
R
6
), S, O or SO
2
.
Suitable linking functionalities for Z
1
include —(CRR)
n
—,—(CRR)
n
—O—(CO)—O—(CRR)
m
—, —(CRR)
n
—O—(CO)—(CRR)
m
—, —(CRR)
n
—O—(CRR)
m
—, —(CRR)
n
—C(═CH
2
)—(CRR)
m
—, —(CRR)
n
—CO—(CRR)
m
—, —(CRR)
n
—(C═O)—, —(CRR)
n
—S—(CRR)
m
—, —(CRR)
n
—SO
2
—(CRR)
m
—, —(CRR)
n
—S—S—(CRR)
m
—, —(O—CRRCRR)
n
— and optionally substituted phenyl (wherein R may vary within the linking functionality and is preferably selected from hydrogen, alkyl, haloalkyl, hydroxyalkyl, hydroxy, carboxy, optionally substituted phenyl, halogen and Z
2
; and m and n are integers including zero).
Suitable linking functionalities for Z
2
in the compounds of the Formula 1b include —G—(CRR)
p
—J—, —G—(CRR)
p
—O—(CO)—O—(CRR)
q
—J—, —G—(CRR)
p
—O—(CO)—(CRR)
q
—J—,—G—(CRR)
p
—O—(CRR)
q
—J—, —G—(CRR)
p
—C(═CH
2
)—(CRR)
q
—J—, —G—(CRR)
p
—CO—(CRR)
q
—J—, —G—(CRR)
p
—(C═O)—J—,—G—(CRR)
q
—S—(CRR)
p
—J—,—G—(CRR)
p
—SO
2
—(CRR)
q
—J—,—G—(CRR)
p
—S—S—(CRR)
q
—J—, —G—(O—CRRCRR)
p
—J—and optionally substituted phenyl (wherein R may vary within the linking functionality and is preferably selected from hydrogen, alkyl, haloalkyl, hydroxyalkyl, hydroxy, carboxy, optionally substituted phenyl and halogen; G and J are functional groups which join Z
2
to Z
1
and may be selected from a bond, —(CRR)
r
—, —O—, NH—, —S—, —(C═O)O—, —O—(C═O)O—, —(C═O)NH—, —NH—(C═O)—O—; and p, q and r are integers including zero). Thus, Z
2
can be derived from di-functional compounds capable of reacting with a functional group, such as, hydroxy, aldehyde, ketone and c

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