USE OF VOIDS OR FILLERS FOR FABRICATING SHAPED ARTICLES FORMED FROM POLYMERS CAPABLE OF EXHIBITING ANISOTROPIC MELTS

Abstract: Shaped articles are provided containing a polymer which is capable of exhibiting anisotropy in the melt and an inert filler characterised in that the inert filler is selected from a) sufficient of a fibrous filler to reduce the anisotropy ratio in the article at least to that obtained from an otherwise similar composition in which the polymer capable of exhibit­ ing anisotropy in the melt is replaced by an isotropic melt forming polymer b) sufficient of a particulate filler to reduce the aniso­ tropy ratio by at least 50% c) at least 10% by volume of voids wherein the anisotropy ratio is the ratio of the stiffness in two directions at right angles in the shaped article.

Description: This invention relates to the use of inert fillers in shaped articles formed from polymers capable of exhibiting anisotropic behaviour in the melt. There has been considerable interest recently in polymers which are capable of forming an anisotropic melt. The interest in these polymers stems from the ordering of the molecules in melts of the polymer. As a consequence of the ordering the melts have a relatively low viscosity giving easy processability and products obtained from the melt have a high degree of orientation leading to enhanced physical properties in the product, such as strength and stiffness. United States Patent No. 4 161 470 and European Patent Publication 8855 describe aromatic polyester resins which are capable of forming anisotropic melts and which may contain particulate and fibrous fillers. In some circumstances a disadvantage of products moulded using an anisotropic melt is the directional imbalance in properties resulting from the high orientation. Shaped articles have now been obtained from anisotropic polymer melts which have taken advantage of the low melt viscosity but in which the anisotropy in the shaped article has been usefully reduced. Accordingly there is provided the use of at least 10% by volume of voids or of fibrous or particulate fillers incorporated into a polymer which is capable of exhibiting anisotropy in the melt for the purpose of fabricating shaped articles having an anisotropy ratio which is reduced by at least 50% in comparison with an otherwise identical article but not containing the specified inert fillers wherein the anisotropy ratio is the ratio of the stiffness in two directions at right angles in the shaped article, the directions chosen to be along and transverse to the flow direction of the melt in forming the article. The ratio of the stiffness in two directions at right angles in the shaped article, termed the anisotropy ratio, is a measure of the extent to which the polymer molecules are aligned in the sample. Preferably the directions should be chosen along and transverse to the principal flow direction of the melt in forming the article. Commonly, melts of anisotropic polymers show much greater stiffness in the flow direction. Typical values for the anisotropic ratio of control samples made from unmodified anisotropic melts are of the order of 4:1 and can be as high as 6:1 or more for highly oriented articles. Desirably this ratio should be reduced to a value of between 0.5 and 2.0. Such products can have a variety of compositions and be made by a variety of methods. By "inert filler" are meant particulate or fibrous fillers, which do not themselves react with the polymer of the composition but does not exclude fillers which have been surface treated to make them more compatible with the polymer matrix. Fillers treated with such surface treatments which react chemically with the polymer matrix are included within the scope of the term. The term includes fillers which have a beneficial effect on the physical properties of the compositions, including for example fillers which improve the strength of articles formed from the compositions. The term "inert filler" also includes holes or voids in the polymer matrix produced by causing the polymer melt to foam. A particularly useful class of fillers are glass fibres in the form of short fibres. The effect of short glass fibres, i.e. fibres of about 2 mm or less in length on the anisotropy ratio is particularly surprising because when used in conventional polymers forming isotropic melts they generally increase rather than decrease anisotropy. By contrast, shaped articles formed according to the present invention containing about 20% by volume of short glass fibres have an anisotropy ratio which is about half that for articles formed from the same composition not containing the filler. Accordingly in one aspect of the invention glass fibres are used in a blend with a polymer which is capable of exhibiting anisotropy in the melt to form a melt of a blend of the polymer and glass fibres and the blend is injection moulded into a shaped article, the blend containing a sufficient concentration of glass fibres to reduce the anisotropy ratio of the resultant moulding by at least 50% in comparison with that obtained from an otherwise identical article not containing the glass fibre. There is also provided the use of particulate filler with a polymer capable of exhibiting anisotropy in the melt to form a melt from a blend of particulate filler and the polymer and injection moulding the blend characterised in that the blend contains a sufficient concentration of particulate filler to reduce the anisotropy ratio by at least 50% of the value obtained from injection moulding a melt consisting of the polymer in the absence of the filler. In a further aspect of the invention the inert filler consists of at least 10% by volume of voids. Thus in a further method of reducing the anisotropic ratio in shaped articles formed from an anisotropic polymer melt the melt is caused to foam in the mould, for example, using conventional foaming agents operative at the temperature of the melt. In this foaming process a foaming agent should be chosen which decomposes to liberate gaseous products within the temperature range over which the anisotropic melt-forming polymer exhibits anisotropic melt behaviour. Accordingly there is provided the use of at least 10% by volume of voids incorporated into a polymer capable of exhibiting anisotropy in the melt for the purpose of fabricating shaped articles having an anisotropy ratio which is reduced by at least 50% in comparison with an otherwise identical article not containing the voids, comprising obtaining an anisotropic melt of the polymer, causing the melt to foam so that it contains at least 10% by volume of voids, forming a shaped article from the foamed melt and quenching the foamed melt. The degree of anisotropy may be assessed by a number of methods which measure properties of a moulding in at least two directions at right angles to each other. A convenient method is to cut a test piece from a shaped article formed in a mould. The test piece should have a square cross-section of 25 mm x 25 mm and have a length of about 100 mm. The test piece should be cut from a region approximately in the centre of the shaped article. The test piece is then further sectioned to cut a slice 1.5 mm thick through the centre of the test piece and running the length of the test piece. The slice is cut to provide samples 1.5 mm x 12 mm x 25 mm. The test pieces are used to measure modulus using a Du Pont Dynamic Mechanical Analyser. Qualitative differences in the degree of anisotropy are readily demonstrated using X-ray techniques. X-ray photos on sectioned samples may be examined using a polar densitometer. X-ray photographs were mounted on a polar table and the intensity traced round the main broad diffraction ring at ϑ=20°, that is Bragg spacing ∿0.45 nm (4.5Å). This diffraction is the result of inter-chain interference and would occur as discrete spots on the equator from a sample of highly oriented fibre. As the orientation is reduced the spots will spread into arcs on the equator. For an unoriented isotropic sample the arcs would merge into a ring of uniform intensity. The invention includes shaped articles and processes in which more than one of the above aspects are combined. The invention is further illustrated by reference to the following Examples. EXAMPLE 1 A sample of copoly-chloro-1,4-phenylene ethylene dioxy-4,4'-dibenzoate terephthalate was made according to Example 3 of United States Patent Specification 3 991 013. The polyester had an inherent viscosity of 0.56 dl/g at 25°C in a 0.5% solution of a mixture of 30% by volume of trifluoracetic acid and 70% by weight of dichloromethane. The polymer was tumble blended with azodicarbonamide (a foaming agent sold under the trade name 'Genetron' (R) AC4) to give a concentration of 1.5% by weight of azodicarbonamide based on the total weight of blend. The composition was injection moulded at 265°C in a 900 g (32 oz) Ankerwerke single screw injection moulding machine using end-gated bar moulds of dimensions 150 mm x 25 mm x 25 mm. The moulding produced had a density of 30% lower than an unfoamed sample prepared from the same polymer. The foam was of the closed cell type with a cell size ranging from about 15 to about 100 µm in diameter. The modulus values, measured along the lengths of the samples, are recorded in the Table below together with values for the unfoamed sample. EXAMPLE 2 A number of compositions were prepared from the polyester used in Example 1 by tumble blending the polymer chip with 3 mm glass fibres (Owens Corning P429YZ) at the concentrations shown in the table below. The compositions were injection moulded on an Arburg injection moulding machine using the indicated conditions. Comparative data on conventional glass fibre filled polypropylene compositions showed that the anisotropy ratio increased from 1 for the unfilled composition to 2 at 30% by weight of glass fibre and to about 3 at 60% by weight of glass fibre. EXAMPLE 3 A composition containing 70% by weight (53.7% by volume) of wollastonite was prepared according to the procedure of Example 2. Test pieces were prepared on the Arburg injection moulding machine using a barrel temperature of 270 to 280°C and a mould temperature of 80 to 90°C. The flexural modulus obtained on a tensile bar was 23.3 GN/m². Values of 18.4 and 14.1 GN/m² were obtained in the 0° and 90° directions on the 115 mm disc giving an anisotropy ratio of 1.3 compared with a value of 4.1 for a control sample containing no wollastonite.

Claims: The use of at least 10% by volume of voids or of fibrous or particulate fillers incorporated into a polymer which is capable of exhibiting anisotropy in the melt for the purpose of fabricating shaped articles having an anisotropy ratio which is reduced by at least 50% in comparison with an otherwise identical article but not containing the specified inert fillers wherein the anisotropy ratio is the ratio of the stiffness in two directions at right angles in the shaped article, the directions chosen to be along and transverse to the flow direction of the melt in forming the article. The use of an inert filler according to claim 1 in which the fibrous filler is glass fibre.

Inventors: BAILEY, DERRICK SIDNEY, COGSWELL, FREDERIC NEIL, GRIFFIN, BRIAN PHILIP
Applicants: IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1981
Main classification: C08K3
IPC codes: C08L67, C08K7, B29C67, B29C70, B29C45, C08G63, B29C44, C08K3