Processable poly(hydroxy acids)

Details Processable poly(hydroxy acids) Processable poly(hydroxy acids)

1995-10-16

2003-05-06

Cain, Edward J. (Department: 1714)

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

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S437000, C525S450000, C524S014000, C524S047000, C524S272000, C524S425000, C524S524000, C524S442000, C524S450000, C524S599000

Reexamination Certificate

active

06559244

ABSTRACT:

This invention relates to poly(hydroxy acid) compositions which have high melt strength and are processable. Especially the invention relates to the use of those compositions in making films.
Biodegradable polymers, biopolymers, constitute a group of materials subject to continual development. Among them are poly(hydroxy acids) which are polymers in which monomers contain both a carboxyl group and a hydroxyl group. Examples of such polymers include polylactic acid (polylactide, PLA), poly(hydroxybutyrate), polyglycolide, and poly(&egr;-caprolactone). Polylactide or polylactic acid, which is most often prepared from lactic acid dimer, lactide, has already for years been used for medical applications like sutures, degradable bone nails or for controlled release of drugs. The molar mass of the polymer in those applications is typically very high and the polymer is purified by dissolving and precipitating it before processing, the thermal degradation is then less. The high price of the polymer and its thermal degradation during processing has limited its use in bulk applications like packaging. It has not been economically profitable to produce and handle the polymer by methods such as those used for medical applications.
Polylactic acid can be produced directly by polycondensation reactions, which are typical in manufacturing of polyesters. However, the highest molar masses are achieved by ring opening polymerisation of lactide. Polylactide is a thermoplastic polyester, which has properties similar to many conventional polymers. However the problem has been that these polymers are difficult to process, and for instance the producing of blown films has not been possible.
The use of polylactides also for other than medical applications has been of special interest lately. A biodegradable, compostable material for hygiene products, agricultural films and packaging applications, either for paper coatings or free films, has been seeked. The reason has been both an aim towards using natural materials instead of fossil raw materials and the good mechanical and barrier properties of polylactides compared to e.g. starch based thermoplastic materials.
Polylactide is a thermoplastic polyester which resembles many conventional polymers.
There is, however, the problem that polymers break down during processing and the molar mass drops considerably. As a result, the useful life of the end products and, partly, their mechanical properties deteriorate. With conventional polymers these problems can be eliminated by using stabilizers. The aim in the use of stabilizers is to maintain the molar mass as constant as possible after polymerization, and in particular also during processing. The change in the molar mass can be monitored by means of, for example, melt viscosity.
Conventional stabilizers, which can be used with aromatic polyesters, are not effective on lactic acid polymers. Boric acid, which, according to German patent application DE 4102170, is used for the stabilization of poly(hydroxybutyrate), does not function with lactic acid polymers.
Certain experiments on various stabilizers have been published. In Japanese patent publication JP68008614, polylactic acids have been stabilized with lactone compounds, such as &ggr;-butyrolactone or &agr;-acetal-&ggr;-butyrolactone. Japanese patent publication JP68002949 describes the adding of isocyanate to improve the heat resistance of lactic acid polymer. These methods have been experimented with, but the results have remained poor.
Attempts have also been made to produce films from pure polylactides, but with no success. Some films have been made by blending with other polymers or from copolymers.
In the German patent application DE 43 00 420 there has been given a blend of polylactide and another aliphatic polyester, preferably polycaprolactone. The polymers are mixed in the melt, granulated and the granules are treated for extended times at temperatures just below melting in order to achieve a transesterification.
The PCT-application WO 92/04493 disclose polylactide compositions with high amount of lactide or lactide oligomers as plasticizing agents in order to achieve flexibility.
In the PCT-application WO 94/07941 melt stable polylactide compositions have been given which are said to be suitable for films. The residual lactide and moisture content have to be very low, and a certain amount of mesolactide must be used in the polymerization. Some “films” are prepared in the example 2 by extrusion of thick sheets. The thicknesses of the tested products is 1-13 mm. Test bars are used in all other examples. Also according to this patent application it is most preferable to use polylactide blends with e.g. polycaprolactone.
Polylactides or copolymers have been made into self-supporting films by casting from solutions or by pressing, as are given already in very old patent publications. As examples are U.S. Pat. Nos. 2,703,316 and 4,045,418.
It is obvious that although many attempts to make films have been made, large scale production based on economical conventional large-scale blown film methods to make thin oriented films has not been possible due to low or missing melt strength of the polymer. If films have been obtained with some method they have been brittle and have had very low elongation at break values unless heavily loaded with palsticizers or blended with other polymeric components.
An other important issue is melt stability. It is well known that polylactides degrade at elevated temperatures during melt processing. Although most mechanical properties would be retained above a certain threshold molar mass, the viscocity decreases drastically and also this makes film blowing of these polymers impossible. Only in the already above mentioned PCT application WO 94/07941 melt stable compositions have been discussed, but even here the melt melt strength is not sufficient for film blowing. The melt stability in that publication is a sum of many different factors and a certain strictly defined polymer composition is needed.
According to the present invention, it has now been observed, surprisingly, that polylactic acids can be stabilized by adding various peroxides to the mixture during processing or as a separate step. By peroxide addition, the scission of chains can be reduced, i.e. the decrease in molar mass can be slowed down. The stabilizing effect of peroxides can also be observed from the melt viscosity value, which, owing to the peroxide addition, decreases during processing considerably more slowly than without peroxide. The effect of peroxides can be manyfold. The catalyst deactivation and end group capping seem to be possible mechanisms. Crosslinking can be neglected, because no gel formation can be observed. The theoretical background of the action of peroxides is outside the scope of this invention.
Further, the object of this invention is to achieve a polylactide composition, which has good melt strength and elongation. Further an object has been to achieve a composition which possesses a melt strength high enough for making films by conventional processing methods, especially by film blowing methods.
In stabilization according to the invention it is possible to use a number of commercially available organic peroxy compounds. Especially suitable are peroxy compounds from which acids are formed as degradation products. It is evident that this acid radical stabilizes the hydroxyl end group of the polymer. Furthermore, it has been observed that peroxides acting as stabilizers are characterized by a short half-life, preferably below 10 s, but most preferably below 5 s. Examples which can be given of suitable peroxides include dilauroyl peroxide (half-life at 200° C. 0.057 s), tert-butylperoxy-diethylacetate (0.452 s), t-butylperoxy-2ethylhexanoate (0.278 s), tert-butylperoxyisobutyrate (0.463 s) and tert-butylperoxyacetate (3.9 s), tert-butylperoxybenzoate (4.47 s) and dibenzoylperoxide (0.742 s). The last-mentioned two have proved to function especially well. It is natural that only a few examples of functioning peroxides were mentione

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