Patent Application
20080033138
The present invention provides a method of producing amine-terminated caprolactone polymers. The polymers produced by the method of the present invention have a number of potential applications.
Amine-terminated polyethers are used as epoxy curing agents in the field of polymer chemistry. In addition, the reaction of amine-terminated polyethers with isocyanates to produce polyurea is an example of the commercial importance of amine-terminated polyethers.
Although amine-terminated polyethers have numerous applications, they are known to have very poor outdoor weatherability due to the ether linkages in the polymer backbone.
There is therefore a need for an alternative polymer with amine finctionality which is less vulnerable to UV and/or oxidative attack that can be used as a replacement to amine-terminated polyethers.
Amine-terminated caprolactone polymers with their ester linkages provide such an alternative due to their comparatively more stable nature. However, although there are a number of known methods for producing caprolactone polymers having a single primary amine group present at a terminal end thereof, there are very few known methods of reliably producing caprolactone polymers having at least two terminal primary amine groups, and thus the use of amine-terminated polyethers is still preferred.
A reaction method to produce a lactone polymer having two terminal primary amine groups is discussed in the Abstract of Japanese Patent Number 63154735.
Such Patent Abstract discloses a three stage reaction process, wherein: 1) the raw material lactone polymer is obtained by ring opening polymerisation of epsilon-caprolactone monomer in the presence of an active hydrogen-containing initiator and a catalyst; 2) the resulting lactone polymer, having either a hydroxyl group on both of its terminals or a hydroxyl group on one terminal and a carboxyl group on the other terminal, is reacted with acid anhydride to produce a lactone polymer with a carboxyl group on each of its terminals; 3) the lactone polymer dicarboxylic acid is then reacted with polyamine to produce the desired polymer.
The amine-terminated lactone polymer produced by the reaction method disclosed in the Japanese Patent Abstract has the following general formula:
H2N—R′—NH—[C(═O)—R—C(═O)—NH—R′]n—NH2 [1]
and where R is a polylactone
A more specific example of an amine-terminated polylactone produced by the above referenced method is:
H2N—(CH2)6—NH—[C(═O)—(CH2)2—C(═O)—O—R—O—C(═O)—(CH2)2—C(═O)—NH—)CH2)6]—NH2 [2]
where R is a polylactone.
Alternative methods of producing amine-terminated polylactones are discussed in earlier publications such as Degee P. et al in Macromolecules(1992, pages 4242-4248). Another prior publication is Stassen S. et al in J. Polym. Sci.: Polym. Chem. (1994, pages 2443-2455). Another publication is Tian D. et al in Macromolecules (1994, pages 4134-4144). Also, Yuan M. et al in Macromolecules (2000, pages 1613-1617); Jeong J. H. et al in Polymer(2002 pages 583-591); and Lu F. -Z et al in Bioconjugate Chemistry(2002, pages 1159-1162).
U.S. Pat. No. 5,525,683 Λ also discloses the preparation of amine-terminated polycaprolactone polymers using methane sulfonyl groups.
The present invention provides a method of producing amine-terminated caprolactone polymers that have at least two terminal ends with a primary amine group thereon.
The method comprises the steps of: firstly using a polycarboxylic acid as an initiator in the ring opening polymerisation of epsilon-caprolactone to produce a polycaprolactone polymer having at least two terminal ends with a carboxylic acid located thereon; and secondly reacting the polymer produced by the first step of the method with a polyamine, at a temperature above 50° C., to produce an amine-terminated polycaprolactone polymer.
Although the reaction between the polycaprolactone polymer, having at least two terminal carboxylic acid groups, and a polyamine can occur effectively above 100° C., the preferable temperature at which the reaction takes place is below 80° C. so as to prevent the reaction of the internal ester groups with the terminal primary amine groups.
Preferably the polyamine used in the second step of the above method is a diamine. However it is appreciated that some triamines and tetramines could also be effectively used. The polyamine used can be liquid, especially in the case of a diamine. An example of a liquid diamine is the commercial product ETHACURE® 100.
Preferably the polycarboxylic acid used in the first step of the above method is a dicarboxylic acid. However it is appreciated that some tricarboxylic acids and tetracarboxylic acids could also be effectively used.
It is appreciated that the functionality of the amine-terminated caprolactone polymer produced by the method of the present invention may be controlled by varying the type of polycarboxylic acid used to open the epsilon-caprolactone ring.
Whilst it is appreciated that the method of the present invention is primarily concerned with the production of caprolactone polymers having two terminal ends with primary amine groups thereon, it is also appreciated that branched caprolactone polymers with more than two terminal ends having primary amine groups thereon can be produced. It is understood that the presence of additional terminal ends is determined by the type of polycarboxylic acid used as an initiator in the ring opening of epsilon-caprolactone. For example, the use of a tri carboxylic acid such as citric acid may be used to introduce a branching into the polymer produced by the splitting of epsilon-caprolactone.
A second embodiment of the present invention provides an amine-terminated caprolactone polymer that has at least two primary amine groups mounted on the terminal ends of the polymer, said polymer having the generic formula:
H2N—(CH2)6—NH CO—CH2)5—O—[C(═O)—(CH2)5—O]n—C(═O)—R1—(═O)—[O—(CH2)5—C(═O)]n—O—(CH2)5—CO—NH—(CH2)6—NH2
where R1═(CH2)pR2; and
R2═CH2 or CH—(CH2)q—(═O)—[O—(CH2)5—C(═O)]s—NH—(CH2)6—NH2 [3]
A third embodiment of the present invention provides uses of the amine-terminated caprolactone polymers of the present invention. One example of a use is as an epoxy resin curative.
Another application of the amine-terminated caprolactone polymers of the present invention is in the production of polyurea, where a reaction with isocyanate can produce a polyurea polymer.
As will be appreciated from the description of the invention thus far, the provided method of producing amine-terminated caprolactone polymers comprises two main stages.
The first reaction stage being the use of a polycarboxylic acid in the splitting of epsilon-caprolactone to produce a polycaprolactone polymer having at least two terminal ends with a carboxylic acid group located thereon. It will be appreciated that a separate catalyst, in the form of an organic acid, would usually be required to promote the splitting of the epsilon-caprolactone ring. However, in some circumstances the role of the catalyst may also be satisfied by the polycarboxylic acid—this appears to be the case with citric acid.
It is appreciated that the size (i.e. Molecular weight—MWt) of the carboxylic acid-terminated caprolactone produced by the first stage reaction is determined by the ratio of the polycarboxylic acid to the monomer. Variation of the catalyst used and other reaction conditions can be used to tailor the size of polymer produced. Examples of preferred ratios of Monomer/Initiator/Catalyst are: 4269 g mono/731 g adipic/5 g catalyst for 1000 MWt; and 4126 g mono/373 g adipic/5 g catalyst for 2000 MWt.
The second reaction stage, which results in the production of the desired amine-terminated caprolactone polymer, involves the reaction of a carboxylic acid-terminated caprolactone polymer with a polyamine at a temperature of 50° C. or above. It is appreciated that the carboxylic acid-terminated caprolactone polymer used in the second stage reaction would be the product of the first reaction stage. However, it will be appreciated that the second reaction stage does not necessarily have to be carried out directly after the first reaction stage.
The reactions may be considered to progress as follows:
A wide range of polycarboxylic acids may be used in the first reaction stage, and it is appreciated that the type of acid used will determine the number of potential terminals on the final amine-terminated caprolactone polymer produced by the method of the present invention.
A preferred selection of polycarboxylic acids include, but are not limited to: adipic acid; succinic acid; dodecanedioic acid; and citric acid.
It is further appreciated that a wide range of polyamines can be effectively used in the second reaction stage. In this regard a preferred selection of polyamines include: Hexamethylenediamine (HMDA); ethylenediamine; N,N′-dimethylethyenediamine; piperazine and piperazine derivatives such as 2-methylpiperazine, 2,5-dimethylpiperazine, 2,3-dimethylpiperazine, 1,4-bis(3-aminopropyl)piperazine and N-aminoethylpiperazine; isophoronediamine; polyoxypropylenediamine; bis(4-amino-3-methyldicyclohexyl)methane; diaminodicyclohexylmethane; bis(aminomethyl)cyclohexane; m-xylylenediamine; alpha- (m-aminophenyl)ethylamine; alpha-(p-aminophenyl)ethylamine; metaphenylenediamine; diaminodiphenylmethane; diaminodiphenylsulfone; norbornenediamine; inclusive of conventional aliphatic, alicyclic, and aromatic amines.
The polyamine is generally used in the second reaction stage as reactant. When the polyamine is liquid, such as the liquid diamine ETHACURE®100, it can be used as diluent, or both as reactant and diluent.
The amount of polyamine used in the second reaction stage can vary in a wide range. It will have an effect on the viscosity of the polymer. In general, the more amine is used, the lower the viscosity of the amine.
A number of experimental examples of both the first reaction stage and the second reaction stage are provided herein after.
First Reaction Stage: Production of carboxylic acid-terminated caprolactone polymers using a polycarboxylic acid to rin g open epsilon- caprolactone monomers.
Analysis of the produced carboxylic acid-terminated caprolactone polymer by Acid Value showed the MWt of the product to be 970.
Analysis of the produced carboxylic acid-terminated caprolactone polymer by Acid Value showed the MWt of the product to be 1795.
Analysis of the produced carboxylic acid-terminated caprolactone polymer by Acid Value showed the MWt of the product to be 1778.
Second Reaction Stage: Production of primary amine-terminated caprolactone polymers by reacting a polyamine with a carboxylic acid-terminated caprolactone polymer.
The total amine content of the resultant reaction mix was analysed by titrating against 0.1M perchloric acid until the methyl violet turns from violet to blue. Results of the analysis showed that the actual primary amine content of the reaction mix was greater that the calculated theoretical primary amine content which suggested the presence of unreacted diamine in the reaction mix.
The total primary amine content of the reaction mix, as measured by titration against perchloric acid, was found to by less than half that of the theoretical amine content. This suggests the occurrence of a reaction between the internal esters groups and the terminal primary amine groups, which was probably due to the temperature increases during the process of the reaction.
Analysis of the reaction product using infra-red spectroscopy revealed presence of peaks relating to primary amines but an absence of peaks relating to diamines.
Analysis of the melting range of the reaction product was noted to be similar to that of other caprolactone polymers.
Analysis of the amine content using the above mentioned titration method suggested that majority of diamine had reacted during experiment.
Analysis of the product of the above experiment provided similar results to those collected from the previous method.
Analysis of the product indicated a completed reaction, although difficulties with the sparging equipment left residual moisture in the mix.
| Number | Date | Country | Kind |
|---|---|---|---|
| 04105098.0 | Oct 2004 | EP | regional |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP05/55306 | 10/17/2005 | WO | 8/2/2007 |
