NUCLEATING AGENT FOR CRYSTALLINE OLEFINIC POLYMERS

Abstract: A nucleating agent for crystalline polymers and copoly­ mers of alpha-olefins, consisting of an aromatic mono­ carboxylic acid or an aliphatic polycarboxylic acid and of a silicate or an alumino - silicate of basic nature, in particular a zeolite, having a refraction index from 1.45 to 1.65.

Description: The spontaneous formation process of the crystalline nuclei in the crystalline polymers and copolymers of the alpha-olefins can be sensibly influenced by the presence of foreign matters of a different type and characterized by a high subdivision and dispersion of the solid particles in the polymeric matrix. The presence of these substances, in suitable concentrations, results in a considerable increase in the number of crystallization nuclei, with consequent increase of the crystallization rate, without any modification of the relevant Avrami's law, which is generally fulfilled by isotactic polypropylene. The increase in the crystallization kinetics is related with a plurality of factors, such as: number and sizes of the nucleating substance particles and chemical-physical characteristics thereof. As the number of particles increases, the system tends to reach a saturation condition in which no further increase in the crystallization rate occurs as a function of the nucleating agent" increment. In the case of polypropylene, the final crystallinity of the nucleated polymer does not substantially differ from the one of the natural polymer; in fact, said final crystallinity prevailingly depends on stereoregularity, molecular weight as well as melting and solidification conditions. The effect caused by the nucleating agents consists therefore in accelerating the crystallization kinetics, without affecting the polymer structural characteristics, with exception of the spherulites'dimension*- which results to be remarkably reduced. Main types of nucleating agents The known nucleating agents can be divided, in relation to their possibile utilizations and to their characteristics, into two basic classes. 1) Non--meltable nucleating agents Among the products most generally used in the industrial practice there are knows the salts of a few organic acids, which, when employed in the form of micropart icles, exhibit a good consistency with the polymer thanks to the presence of the organic moiety in their molecule. These substances, however, involve great difficulties as regards dispersion, which are due both to the me thods employed for incorporating them into the polymer ic matrix, and to the average size of their particles, to the particle-size distribution, to the physical form and purity. All these factors concur to justify a certain inconstan cy at their nucleating power. The most commonly utilized products include the salts of alkaline metals, earth-alkaline metals and of al uminium, of the gluconic, succinic, adipic, benzoic, p-ter.butyl benzoic acids, etc. The use of organic acid salts, generally endowed with a good nucleating power, does not always permit to ob tain an excellent transparency of the manufactured art icles. This depends on the difficulty of obtaining the above said products with particles of submicronic dimensions, as well as on the value of their refraction index, which is by far different from that of the polymeric substrate. 2) Meltable nucleating agents To this class belongsa certain number of organic com pounds characterized by a melting point which is lower than the polymer processing temperature, by a good consistency with the polymer and by the capability of crystallizing, in the form of microparticles, originat ing a very high number of hqmogeneously Subdivided crys tallization nuclei. A group of compounds which, due to the chemical nature and nucleating properties, appears particularly interesting, consists of a few organic acids selected from amongst the aliphatic polycarboxyl ic acids and the aromatic monocarboxylic acids. The use thereof, however, is substantially hindered by the cor rosive power they impart to the polymer into which they are incorporated. A further limitation is represented by the inconstancy, in terms of nucleating efficiency, caused by their interacting with catalytic residues and additives cont ained in variable amounts in the polymer and in partic ular with the glyceryl monostearate employed as process coadjuvant. Nucleating composition according to the invention It has now been found, and this forms the object of the present invention, that it is possible to overcome the problems of dispersion, corrosiveness and inconstancy in the nucleation by employing a nucleating composition consisting of a) an organic acid selected from the aromatic monocarbo xylic acids and the aliphatic polycarboxylic acids; b) an inorganic compound acting as a neutralizing agent of the carboxylic acid and selected from the simple or mixed silicates of the metals belonging to Groups I and II of the Periodic System and relevant alumino sil icates, characterized by a basic nature and a refract ive index ranging from 1.45 to 1.65. Non-limitative examples of the abovesaid compounds are: - aliphatic polycarboxylic acids with preferably 2 or 3 carboxylic groups such as: glutaric-acid succinic acid adipic acid and aromatic monocarboxylic acids preferably those of the benzene or naphthalene series such as benzoic acid toluic acid p-tert.butyl-benzoic acid - for the inorganic compounds : sodium silicate magnesium silicate calcium silicate sodium and calcium silicate magnesium and calcium silicate sodium and aluminium silicate hydrated or anhydrous alumino silicates of Na, X, Ca, NH4 comprising, in particular, the synthetic zeolites of gen eral formula : Mx/n.(AlO2)x.(SiO2)y.zH2O wherein n = the valence of the alkaline or earth-alkaline element S. The synthetic zeolites may be classified, depending on the value of the 3iO vA1203 ratio, according to the 23 scheme SiO2 zeolite Awl 203 type 2 A 2.4 x 4.8 Y 50 ZSK Furthermore, the zeolites of type A, depending on the metal cation K, can be aivided into : CATION ZEOLITE 3A ZEOLITE 4A Na+ ZEOLITE 5A Ca ZEOLITE NH4 NH4 4 The concentration of the nucleating composition may range from 0.05 to 2.0% by weight and, preferably, from 0.1 to 0.6% , the weight ratio between inorganic compound and organic acid being possibly comprised between 0.5 and 10 and, preferably, between 2 and 6. The nucleating systems forming the object of the present invention prove to be chemically inert with respect to the polymeric substrate, do not induce corrosiveness into the polymer and, besides, their effectiveness is not affected by the presence of catalyst residues or of additives, in particular of glyceryl monostearate. The alkaline or earth-alkaline silicates and the corresponding alumino-silicates being part of the nucleating compositions of the present invention are non-toxic and are accepted by the Italian regulations as additives of polymers intended for coming into contact with food. Also some inorganic acids included among the ones listed in the present patent have proved to be non-toxic, wherefore it is possible to form nucleating systems provided with toxicity-free properties. The ingredients of the nucleating composition can be additioned to the polymer along with the components of the stabilization formula, by employing the conventional techniques adopted in the industrial practice. The evaluation of the nucleating power of the compositions object of this invention is accomplishedfin terms of crystallization temperature (CT OC) measured by DSO (differential scanning calorimetry) techniques, and of optical characteristics (Haze) determined by method ASTM D-1003/A. The higher the CT value, the higher the nucleation degree of the polymer. Since the nucleation can raise the crystallization temperature by 20-25 C, it is apparent that a considerable advantage in terms of a higher cycle productivity is achiev ed in the injection molding processes. The transparence of the manufactured articles results the higher, the lower the Haze values are. The CT data are determined on die-cast platens having 1 mm thickness, produced from the granulated polymer. The Haze data, conversely, are determined on die-injected platens, also 1 mm thick. The tests indicated in the following examples have been carried out by using industrially produced iso tactic polypropylene additioned with 0.05% of 2,6-di-tert.butyl-p.cresol as a process stabilizer, and with 0.05% of IRGANOX 1010, an antioxidant of the phenolic type consisting of tetramethylene-(4'-hydroxy-3',5'-di-tert.butyl-phenyl propionate)methane. The presence of other additives is specifically in dieted in the relevant examples. Examples 1-19 2-kg samples of powdered isotactic polypropylene (MIL = 3.0) were homogenized in a centrifugal mixer with the stabilizers ana the nucleating compositions based on organic acid and inorganic compound. The powders were successively fed to a single-screw extruder and granulated at a temperature of 2300C, molding by die-casting and die-injection the platens for the CT and Haze determinations. The behaviour of the different nucleating systems is illustrated in the following Table 1. T A B L E 1 EMI9.1 EXAMPLE <SEP> ORGANIC <SEP> ACID <SEP> (A) <SEP> INORGANIC <SEP> COMPOUND <SEP> (B) <tb> GMS.(2) <SEP> B/A <SEP> A <SEP> + <SEP> B <SEP> C@ <SEP> HAZE <SEP> VISUAL <tb> NO <SEP> CORROSIVENESS <tb> TYPE <SEP> pH <SEP> (1) <SEP> (% <SEP> b.w.) <SEP> (weight) <SEP> (% <SEP> b.w.) <SEP> ( C) <SEP> (%) <SEP> EVALUATION <tb> 1 <SEP> - <SEP> - <SEP> - <SEP> 0,07 <SEP> - <SEP> - <SEP> 104 <SEP> 75 <SEP> opaque <SEP> middle <tb> 2 <SEP> benzoic <SEP> acid <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 0,1 <SEP> 118 <SEP> 58 <SEP> little <SEP> transparent <SEP> strong <tb> 3 <SEP> " <SEP> " <SEP> - <SEP> - <SEP> 0.07 <SEP> - <SEP> 0,1 <SEP> 110 <SEP> 70 <SEP> opaque <SEP> strong <tb> 4 <SEP> " <SEP> " <SEP> zeolite <SEP> 4A <SEP> 10,8 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 118 <SEP> 60 <SEP> little <SEP> transparent <SEP> none <tb> 5 <SEP> p-tert.butyl <SEP> ben- <SEP> - <SEP> - <SEP> 0,07 <SEP> - <SEP> 0,2 <SEP> 117 <SEP> 98 <SEP> opaque <SEP> strong <tb> zoic <SEP> acid <tb> 6 <SEP> " <SEP> " <SEP> " <SEP> zeolite <SEP> 4A <SEP> 10,8 <SEP> 0,07 <SEP> 1,5 <SEP> 0,5 <SEP> 124 <SEP> 44 <SEP> transparent <SEP> slight <tb> 7 <SEP> succinic <SEP> acid <SEP> - <SEP> - <SEP> 0,07 <SEP> - <SEP> 0,1 <SEP> 113 <SEP> 70 <SEP> opaque <SEP> strong <tb> 8 <SEP> " <SEP> " <SEP> zeolite <SEP> 4A <SEP> 10,8 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 121 <SEP> 44 <SEP> transparent <SEP> none <tb> 9 <SEP> " <SEP> " <SEP> " <SEP> 3A <SEP> 10,7 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 120,5 <SEP> 44 <SEP> transparent <SEP> none <tb> 10 <SEP> " <SEP> " <SEP> " <SEP> " <SEP> 10,7 <SEP> 0,07 <SEP> 2 <SEP> 0,3 <SEP> 121 <SEP> 43 <SEP> transparent <SEP> slight <tb> 11 <SEP> " <SEP> " <SEP> " <SEP> NH4 <SEP> 9,6 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 121 <SEP> 43 <SEP> transparent <SEP> none <tb> 12 <SEP> " <SEP> " <SEP> " <SEP> 5A <SEP> 10,0 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 120 <SEP> 43 <SEP> transparent <SEP> none <tb> 13 <SEP> adipic <SEP> acid <SEP> - <SEP> - <SEP> 0,07 <SEP> - <SEP> 0,1 <SEP> 115 <SEP> 65 <SEP> translucid <SEP> strong <tb> 14 <SEP> " <SEP> " <SEP> zeolite <SEP> 4A <SEP> 10,8 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 123,5 <SEP> 35 <SEP> very <SEP> transparent <SEP> none <tb> 15 <SEP> " <SEP> " <SEP> " <SEP> " <SEP> 10,8 <SEP> 0,07 <SEP> 6 <SEP> 0,7 <SEP> 120 <SEP> 46 <SEP> transparent <SEP> none <tb> 16 <SEP> " <SEP> " <SEP> " <SEP> 13X <SEP> 11,0 <SEP> : <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 122 <SEP> 42 <SEP> transparent <SEP> none <tb> 17 <SEP> " <SEP> " <SEP> Na <SEP> and <SEP> Al <SEP> silicate <SEP> 11,2 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 122,5 <SEP> 40 <SEP> transparent <SEP> none <tb> 18 <SEP> " <SEP> " <SEP> Na <SEP> and <SEP> Mg <SEP> silicate <SEP> 9,8 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 123,5 <SEP> 36 <SEP> very <SEP> transparent <SEP> none <tb> 19 <SEP> " <SEP> " <SEP> Na <SEP> and <SEP> Ca <SEP> silicate <SEP> 10,1 <SEP> 0,07 <SEP> 3 <SEP> 0,4 <SEP> 124 <SEP> 35 <SEP> very <SEP> transparent <SEP> none <tb> (1) .The pH value was measured in the aqueous dispersion of the product at a concentration of 1% by weight, at 20 C. (2) GMS = glyceryl monostearate.

Claims: Claims 1. Nucleating agent for crystalline polymers and copo lymers of alpha-olefins, consisting of the combination of : a) an aromatic monocarboxylic acid or an aliphatic polycarboxylic acid, b) a silicate or an alumino-silicate of metals of the 1st or 2nd Group of the periodic system, suit ed to neutralize the carboxylic acid and having a refractive index of from 1.45 to 1.65, in which combination the weight ratio of component b to component a ranges from 0.5 to 10, the nucleating agent being used in amounts equal to 0.05% and up to 2% by weight referred to the polymer. 2. The nucleating agent according 'GO claim 1, wherein component b consists of a zeolite0 3. The nucleating agent according to any of the preceding claims, wherein the weight ratio between component b and component a ranges from 2 to 6. 4. The nucleating agent according to any of the preceding claims, employed in amounts corresponding to 0.1% and up to 0.6% by weight referred to the polymer.

Inventors: CASELLI, GIANCARLO, GORINI, GIUSEPPE
Applicants: MONTEFINA S.A.
Application year: 1983
Main classification: C08K3
IPC codes: C08K5, C08K3