JPS6043378B2 - Multiphasic polyamide composition with improved impact strength properties and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to polyamide substrate compositions that combine very good thermal stability with improved properties of impact strength, ductility and crystallization, and processes for the production of these compositions. .

Unmodified polyamides with high fracture energies are considered tough polymers.

In contrast, they generally lack resistance to fracture propagation due to cracking and embrittlement, which is the result of some degree of notch brittleness. This drawback of failure in brittleness rather than ductility greatly limits their use and reliability. Improvements in the impact strength of thermoplastic polyamides have been studied in detail and many solutions have been proposed.

For example, British Patent No. 99843? is made from a mixture of 50-99% linear polyamide and 1-50% olefinic copolymer dispersed in particulate polyamide having 0.1-10 mol% acid groups and having a diameter of less than 5μ. The company has obtained rights to the composition. U.S. Patent Nos. 33, 186 and 34
No. 650 patents a mixture of polycaproamide and an olefinic copolymer containing 1 to 20 mol % of (meth)acrylic acid or a derivative thereof grafted with an amino acid.

U.S. Pat. No. 3,668,274 discloses that polyamide and
A first elastomer phase (50 to 50%) grafted with a highly rigid copolymer having 1 to 5% unsaturated carboxylic acid
99.9% alkyl acrylic ester and butadiene) multiphase polymer having a carboxy group 2.5~
A mixture with 30% is described.

U.S. Pat. No. 3,845,163 discloses polyamide 60
α-olefinic copolymers containing 1 to 8 mol % of α,β-ethylenic carboxylic acids in which at least 10% of the acid groups are neutralized by metal ions
A mixture with 4% saliva volume is described.

French Patent No. 2,311,814 claims a very large number of multiphase polyamide compositions with improved toughness, which contain particles of 60-9% polyamide and at least one other polymer. Phase 1~
consisting of a mixture manufactured in the molten state with 4% weight,
The at least one polymer has a modulus under traction of one order of magnitude of that of the polyamide, "sticks" to the polyamide, and has a particle size of 0.01 to 3 microns. Polymers which can be used as the dispersed phase are selected from non-crosslinked linear or branched thermoplastic or elastomeric polymers belonging to the following chemical classes: unsaturated monomers, copolymers with molecules that generate functional sites, such as carbon monoxide, carboxylic acids or derivatives thereof with α,β monoethylenic unsaturation, unsaturated epoxides and aromatic sulfonyl azides substituted with pentacarboxylic acids; A polyurethane derived from a polyester-glycol or a polyether-glycol; and a polyether)-tel network polymer obtained by reacting an epoxide monomer.

Many of the polymeric additives mentioned in the prior art have relatively low thermal or chemical stability, which limits their use to the field of conventional polyamides, where the manufacturing or processing conditions are extremely harsh. For example, French Patent No. 231
The polyurethane and polyether network polymers described in No. 1814 can only reasonably be used in the case of matrices with melting points below 200-220°C. A very large number of copolymers of olefins and acrylic derivatives described in the prior art show very significant decomposition in the melt when mixed with polyamides having a high melting point, such as polyhexamethylene adipamide. receive.

The use of polyamides with good thermal stability together with a polyamide matrix as reinforcing phase for thermoplastic compositions has not been previously described.

Conventional polyamides or copolyamides, such as, but not limited to, mention may be made of polycaprolactam, polyhexamethylene adipamide, polyhexamethylene sebacamide, polyhexag-methylene dodecanamide and copolymers thereof. Mixtures of , in fact, have a well-known chemical instability in the molten state, which is based on the existence of exchange reactions between different types of amide sequences. For example, it is generally not possible to obtain stable dispersions of polyamide or copolyamide particles in other polyamides in the molten state. Systems of this type necessarily transform more or less rapidly from polyamide blocks into homogeneous copolyamides initially formed, which themselves transform more or less rapidly into more or less random copolyamides. Polyamide additives have been found in the prior art that are used to modify other polyamides, but whose purpose is not to create stable multiphase compositions.
These polyamide additives are different from those of the present invention. U.S. Pat. No. 3,645,932 describes the use of polyamides derived from polymeric fatty acids with 0.1 to 1 weight percent of nucleating agents, which may be other polyamides that generally have a high melting point and a high tendency to crystallization. Nuclear formation is legalized. U.S. Pat. No. 40,628 has improved rheological properties and flowability and has a polyamide resin of 80-99.99% and a heel weight % of less than 3. and an aliphatic or cycloaliphatic diacid having 18 to 52 carbon atoms; and saturated aliphatic diacids having 2 to 13 carbon atoms (this is the 30
% by weight) and a polyamide additive obtained by reaction with a stoichiometric amount of one or more saturated aliphatic diamines having from 2 to W carbon atoms. It has become

The polyamide additives described have relatively high melting points and are substantially compatible with the base polyamide resin. The resulting composition has improved flowability, slightly greater flexibility and a crystallization rate that is not much lower than matrix formation when the proportion of additives does not exceed 10%. The impact strength of these compositions is not much greater than that of the pure basic polyamide. In the case of polyamide 6,6, the impact strength is reduced by 14% with the presence of 2% additive, whereas in the case of polyamide 6 this increases by 9.5% with 2% additive and with 10% additive This decreases to 15.5% lower than that of . A polyamide-based multiphase composition has now been found that has improved physical properties and is particularly stable at high temperatures, which composition comprises a matrix-forming phase that is a polyamide resin and a first polyamide resin. and at least one other dispersed phase that is incompatible with the dispersed phase.

The matrix-forming phase advantageously has a number average molecular weight of at least 5000. The other dispersed phase is 0.001 to 1
It is in the form of particles having a size of 0.00μ, preferably a size of 0.01 to 10μ. This other dispersed phase consists wholly or partly of a polymer selected from polyamides.

These polyamides advantageously contain less than 40%, preferably 20%, of the amide groups of the matrix-forming polyamide resin.
It has a proportion of amide groups of less than %. If the amide group content of polyamide is 40% of the amide group content of nylon polyamide resin,
%, the two types of polymers, nylon polyamide resin and polyamide resin, tend to be compatible. As a result, subjecting the matrix phase and the particulate dispersed phase to shear conditions results in a homogeneous mixture in which the particulate dispersed phase is unable to reinforce the matrix phase. The polyamide selected has a glass transition temperature of less than 5°C, preferably less than -10'C. These multiphase compositions consist of 50-9% heel weight matrix and 1-5 % heel weight dispersed phase.

Advantageously, these multiphase compositions consist of 55-9 weight percent matrix and 1-45 weight percent dispersed phase.
In another aspect, the invention relates to a particular method developed for producing the compositions of the invention.

The term multiphasic composition is understood to mean a composition consisting of at least two phases that remain distinct in both a solid state and a molten state. A distinction is made between the main phase or matrix and the reinforcing phase or phase dispersed within said matrix. The expression "becomes more substantial" means that other components besides the matrix-forming polyamide dispersed phase may be present in the composition; provided that these components do not contribute to the essential properties of the composition. shall not be substantially changed.

The expression "at least one other dispersed phase in the form of particles with dimensions between 0.01 and 10μ" means
This is understood to mean that at least one dispersed phase in the form of particles with a maximum dimension of 0 μ is present in the composition based on a polyamide corresponding to the above definition.

One or more other polymers in the form of particles of 0.01 to 10 microns may also be present in some minor proportion.

The expression "consisting wholly or partly of a polymer selected from polyamides" means that one or more polyamides corresponding to the above definition constitute the dispersed phase and the essential properties of the composition are not impaired. This means that it may also contain a certain proportion of other polymers.

In addition to the polyamide dispersed phase, these other polymers in small proportions which may be present in the dispersed phase may consist, for example, of reinforcing polymers as described in the patent specifications mentioned above as prior art. The matrix-forming polyamide resins in the compositions of the present invention are resins well known in the art and include semicrystalline and amorphous resins having a molecular weight of at least 5000 and commonly referred to as nylons.

Polyamides that can be used include U.S. Pat. No. 2,071,250;
No. 2071251, No. 2130523, No. 2130
No. 948, No. 2241322, No. 2312966,
It includes those described in each specification of No. 2512606 and No. 33932m. This polyamide resin has 4
a saturated dicarboxylic acid having ~12 carbon atoms and 4 to 1
It can be produced by condensing equimolar amounts with a diamine having two carbon atoms. Excess diamine can be used to obtain an excess of amino end groups relative to carboxyl end groups in the polyamide, or an excess of diamine may be used to obtain an excess of carboxyl end groups relative to amino end groups in the polyamide. diacids can also be used. Chain terminators are usually used in order to be able to control the molecular weight of the resulting polymer.

This chain stop. The inhibitor is used in an amount corresponding to the desired molecular weight range. However, generally 0.1 to 2 mol% of salt is used. The chain terminator is selected from the group consisting of carboxylic acids and aliphatic amines.

Examples of polyamides are polyhexamethylene adipamide (nylon-6,6), polyhexamethylene azeramide (nylon-6,9), polyhexamethylene sebamide (nylon-6,10), and polyhexamethylene dodecanamide (nylon-6,10). 6,12), polyamides produced by 1 upon ring opening of lactams, namely polycaprolactam and poly(lauryllactam), poly(11-aminoundecanoic acid) and polybis(p-aminocyclohexyl)
Includes methandecanamide. In the present invention, it is also possible to use polyamides produced by copolymerization of two of the above-mentioned monomers or by terpolymerization of constituent components of the above-mentioned polymers, such as adipic acid, isophthalic acid, and hexamethylene diamine. Preferably the polyamide is linear and has a melting point above 200°C. The polyamide constituting the reinforcing phase, ie the phase dispersed in the matrix, is a linear, branched or crosslinked polyamide or copolyamide.

In the latter case, the crosslinking must be such that the glass transition temperature (Tg) does not exceed 5° C. and must be carried out in such a way that the particle size according to the invention is obtained.
A simple method for producing a composition having a crosslinked dispersed phase is described in this application. Linear polyamides or copolyamides which can be used as reinforcing phase are obtained by polycondensation of mixtures of lactams or lactums, diacids and diamines, or mixtures of diacids and diamines. The diacids or diamines used optionally contain one or more heteroatoms in their chain, such as oxygen (in which case an ether or polyether bond is obtained), sulfuric acid (in which case a thio or polythio bond) or nitrogen (in which case an imine or polyimine bond is obtained). They can optionally also have one or more double bonds. Used as reinforcing phase Branched or crosslinked polyamides or copolyamides which may be of the same type as used for linear polyamides or copolyamides, but which contain at least three reactive groups, some of which are of the same or different type. Since the polyamides according to the invention must have a proportion of amide groups of less than 40% of the amide groups of the matrix, they are obtained from reactants such that at least one of the monomers It must be prepared using monomers having a molecular weight at least 2.5 times greater than the average molecular weight of the monomers.By way of non-limiting example, depending on the nature of the matrix selected, polymer dioxide and/or diamides, or polyether diamines or -diacids can be used.The high molecular weight long chain diacids and diamines that can be used according to the invention can be aliphatic or cycloaliphatic; and these have more than 18 carbon atoms.The chain can be linear or, if desired, can also have alkyl branches.In the case of substantially linear polyamides or copolyamides, industrial The dicarboxylic acids used can also contain small amounts of mono- and/or polyacids, but the proportion of diacids is 80
Must be greater than %. Dicarboxylic acids of particular value in the present invention are acids obtained by dimerizing fatty acids having 16 to 2 carbon atoms, such as, for example, oleic acid, linoleic acid, linolenic acid or oleostearic acid or mixtures thereof. .

Of particular value are the diacids obtained by dimerizing acids of Cl8, such as oleic acid or linoleic acid or mixtures thereof. These dimeric acids necessarily contain a proportion of monocarboxylic or polymeric acids, the latter being predominantly trimeric acids.

Preference is given to using dimer acids having a proportion of dimer greater than 9% by weight.

Similarly, diamines used industrially can contain a certain proportion of monoamines and/or polyamines.

Polyamines of particular value in the present invention are polyamines with 32 to ω carbon atoms, which are obtained from dimers of fatty acids with 16 to 2 carbon atoms, with a certain proportion of monomeric amines and (or) may contain polymerized amines, the latter being primarily trimeric amines. It is advantageous to use dimeric diamines with a proportion of dimer greater than 9% by weight. In the case of branched or crosslinked polyamides or copolyamides according to the invention, which are of value in certain cases, reactants having at least three reactive groups can be used to prepare these polyamides or copolyamides. Non-limiting examples are: triamines, such as for example bishexamethylene triamine, or trimeric amines obtained from trimers of fatty acids having from 16 to 2 carbon atoms; for example 16 Triacids such as trimers of fatty acids with ~2 carbon atoms, 1,
2,4-benzenetricarboxylic acid and 1,3,5-benzenetricarboxylic acids, such as tetracarboxylic acids such as 1,2,4,5-benzenetetracarboxylic acid; unsaturated acids, in particular e.g. itaconic acid; In the latter case, crosslinking is achieved by polymerizing double bonds, which generally requires the presence of an initiator or an unsaturated comonomer.

However, the polyamide used as reinforcing phase
It does not contain any order obtained by condensation reaction other than the amide order.

Other polymers which may form part of the composition of the dispersed phase according to the invention are generally fully or partially miscible with the polyamide used for the dispersed phase within a temperature range of 200-300°C. It is a moist polymer.

Polymers corresponding to this property and having functional groups reactive towards polyamides are of particular value as crosslinking agents for the polyamides used as the reinforcing phase of the present invention. Of course, the compositions according to the invention may also contain one or more additives, such as stabilizers and inhibitors of oxidative, ultraviolet or photo- or thermal degradation, lubricants and mold release agents, coloring substances consisting of dyes and pigments, fibers. It can also be modified with granular fillers and reinforcing agents, nucleating agents, plasticizers, etc.

Stabilizers can be incorporated into the thermoplastic composition at any stage of manufacturing the composition. Preferably, the stabilizer is included fairly early to prevent the composition from degrading from the start before it can be protected. These stabilizers must be compatible with the composition. Oxidative and thermal stabilizers that can be used in the materials of the invention include those commonly used in polyamides.

These include, for example, halides of group 1 metals such as sodium, potassium and lithium, copper halides such as chlorides, bromides and iodides, sterically hindered phenols, up to 1% by weight, based on the weight of the polyamide;
Includes hydroquinolines, as well as various substitutions of these types and combinations thereof. For example, UV stabilizers present in proportions of up to 2% by weight of the polyamide may normally be used with the polyamide.

Examples that may be mentioned are various substituted resorcinols, salicylic acid compounds, benzotriazoles, benzophenones, etc. Lubricants and mold release agents which may be used, for example, in proportions up to 1.0% by weight of the composition are stearic acid, stearyl alcohol and stearylamide, and also organic dyes and pigments such as titanium dioxide, carbon black, etc. It can be used in proportions up to % by weight.

Fibrous or particulate fillers and reinforcing agents, such as carbon fibers, glass fibers, amorphous silica, asbestos, calcium silicate, aluminum silicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, fluorite, etc. , may be present in proportions up to 50% by weight of the composition, as long as the desired mechanical properties are not substantially impaired.

The composition further comprises nucleating agents such as talc, calcium fluoride, sodium phenylphosphinate, alumina and finely divided polytetrafluoroethylene, and plasticizers,
For example, dioctyl phthalate, dipendyl phthalate, butylbenzyl phthalate, hydrocarbon oil, N-n-butylbenzenesulfonamide, o- and p-toluene-ethylsulfonamide, etc., up to about 20% by weight of the composition. It can also be contained in a proportion of

According to another aspect of the present invention, there is provided a method of manufacturing a polyamide-based multiphase composition according to the present invention.

In the first method, 55 to 99
% by weight of at least 5000, preferably 10000
a matrix-forming polyamide resin having a higher number average molecular weight; and 1 to 45% by weight of at least 2
one or more reinforcing polymers consisting of a polyamide having a nominal weight % of a glass transition temperature of less than 5° C. and a proportion of amide groups of less than 40% of the amide groups of the polyamide resin used as the matrix; At a temperature above the melting point of the polyamide resin used as the matrix, 0.01 to 10 μm of reinforcing polymer is added into the matrix.
The reinforced polyamide is mixed in a closed system under shear conditions such that it can be dispersed as particles of such size that the reinforced polyamide is linear or slightly crosslinked. The number average molecular weight of the reinforced polyamide is greater than 5000, preferably 15000
Must be bigger. Shear conditions are generally difficult to determine. This depends in particular on the melting point of the polyamides present and their melt viscosity at the working temperature.
The determined shearing time can be substantially influenced by the equipment, ie the number of screws, the shape of the screws, the separation of the extruder from the barrel, etc. Optimal conditions can only be determined by experiment.

In a variant of this first method, 55 to 9 weight percent of a matrix-forming polyamide resin having a number average molecular weight of 2000 to 10000, based on the mixture of polymers;
45% by weight of one or more reinforcing polymers of which at least 2% a consists of a polyamide having a molecular weight greater than 5,000, preferably greater than 15,000; The reinforcing polymer is incorporated in a system that allows degassing at a temperature above the melting point of the resin and under conditions that allow the reinforcing polymer to be dispersed in the matrix as particles with a size of 0.01 to 10 microns. The polyamide must have a glass transition temperature of less than 5° C. and contain amide groups in a proportion of less than 40% of the amide groups of the polyamide resin used as matrix. The dispersion of the reinforcing polymer and the completion of the polycondensation of the polyamide used as matrix therefore take place simultaneously.

As mentioned above in this method, it is difficult to specify the shear conditions "in general", which depend not only on the nature and relative amounts of the matrix-forming polymer and the polymers used as reinforcing phase, but also on temperature. It also depends on the device.

A factor which can be particularly easily varied is the operating time, which must be able to complete the polycondensation of the matrix and the dispersion of the reinforcing phase. Other variations of this method are of particular value if the components of the reinforcing polyamide, ie polyamines, polyacids or salts thereof, are highly incompatible with the components of the matrix polyamide.

The main components (diamines, diacids and/or salts) or oligomers with a molecular weight of less than 500 of the polyamide used as matrix and of the reinforcing polyamide are incorporated into a system that allows polycondensation of the polyamide. Polycondensation is
It is carried out and completed by methods commonly used for the production of matrix-forming polyamides. However, the equipment used is equipped with a stirrer that allows the two phases to be dispersed in one another. The nature and amount of the components of the reinforcing polyamide are such that the polyamide obtained from these components has a glass transition temperature of less than 5°C and contains amide groups in a proportion of less than 40% of the amide groups of the polyamide resin used as the matrix. It is obvious that one must choose to have one.

Furthermore, in this variant the operating conditions are important.

This is because, as mentioned above, in this variant method, it is necessary to carry out both dispersion and polycondensation. lastly,
Other variations are particularly valuable if the reinforcing polymer is soluble in the major component or oligomer of the matrix-forming polyamide at temperatures below about 200°C.

The reinforcing polyamide with a molecular weight of more than 5000, preferably more than 15000, is dissolved in the main component of the matrix polyamide or in the oligomer, and the polycondensation of the matrix polyamide is completed in a customary manner under stirring.

The reinforcing polyamide must have a glass transition temperature of less than 5° C. and a proportion of amide groups that is less than 40% of the amide groups of the polyamide resin used as matrix.

The reinforcing polyamide precipitates as a second dispersed phase as the molecular weight of the matrix polyamide increases.

As can be seen from the description of the above method and its variants, it is not possible to use any method with any matrix and any reinforcing phase.

Certain selections are possible, but this will depend on the nature of the various ingredients,
So! It depends on their respective proportions and the desired properties of the final composition. The reinforced thermoplastic compositions can be molded into a variety of useful articles, such as molded articles, extrusions, etc., by conventional compression molding or extrusion methods used in the manufacture of thermoplastic articles. Products such as tubes, films, sheets, fibers and oriented fibers,
It can be changed into a laminate, wire coating, etc.

The composition according to the invention is characterized by a remarkable combination of properties, the most important of which is a pronounced toughness and a tendency to crystallization, taking into account the amount of reinforcing polymer present together with the polyamide matrix. .

The toughness, which can be significantly higher, results in high ductility and significantly reduced susceptibility to notches caused by forming. A very large number of applications in the field of engineering can be realized.

The following examples illustrate various D methods and compositions developed in accordance with the present invention.

In these examples, several tests were performed on major surface component y of polyamide.

Similarly, various properties as well as composition were measured. The procedures or details for conducting these tests are shown below. 1 PH measurement of dilute solutions of dimer acid/hexamethylene diamine (1Ir!4D) salts Radiometer PHM6 with glass/calomel combination electrode? P.H.
Use a meter.

Measurements are carried out at 20°C. The device is calibrated using two buffer solutions, pH 7 and 9, and scanning the pH corresponding to the dimer acid/HFIMD salt equivalence point.

The PH is determined by preparing the salt as a 50% strength solution in a 50/5 stoichiometric mixture of water and isopropanol and bringing the salt concentration to 10% in the same solvent mixture.

PH is the value of P corresponding to the equivalence point (i.e. 8.75)
Adjust within the range of ±5/100 of H units.

), the conditioning reinforcement phase of the polymer in EHO (zero):
The reinforcing phase is heated in the open at ambient temperature from 0.5 to 1 column of mercury.
Dry for 24B1 over P2O5 under vacuum of Tnm.
The polymer used as the matrix is
It was dried in an open chamber at 1100 C under reduced pressure of 0.5 to 1 bar of mercury for an hour.

The molded test piece is placed in a desiccator containing silica gel, and the mercury column is 0.5 to 1 cm before measurement. Drying was continued for two more hours at ambient temperature under reduced pressure.

Flexural Modulus at EHO and 23° C. This measurement is carried out on injection molded 80×10×4w0n bar specimens according to the ISO recommended standard Rl78.

Notch impact strength Charpy notch impact strength, ISO recommended standard Rl79
Measure according to.

The measurements are carried out on shaped rods with the following dimensions: length 50 ± 0.1? , width 6±0.2 order, thickness 4±0.2Tr
$L1 notch length 0.8±0.1Tn! Thickness below n1 notch 2.7±0.2T! A RInO Zwick impact meter was used at 23° C., and the specimens were conditioned in EHO.

Results are expressed in J/Cll.

Determination of the 5-end machine A solution of the polymer in a 90/1 volume mixture of NH2:phenol and water is autopotentiometrically measured using HCI.

Results are expressed as y equivalents per 1 Cf'V of polymer. C.O.
OH: The polymer is dissolved by heating in benzyl alcohol under a nitrogen atmosphere, and the hot solution is acid titrated with a glycol solution of potassium hydroxide under a nitrogen atmosphere in the presence of phenolphthalene.

The results are expressed as y equivalents per 1 Cf'y of polymer. 6 Determination of Intrinsic Viscosity The dry polymer is dissolved in m-cresol to obtain a 0.5% strength solution.

The efflux time of this solution is determined compared to that of the pure solvent. , the value of the intrinsic viscosity is given by the following formula: It is characterized by the conversion point (CpC) (the difference between the two constitutes the supercooling Δ which characterizes nucleation).

Another crystallization property that is essentially related to crystal growth rate is Tg
It is based on the measurement of α, where α is formed by the horizontal plane of the baseline and the initial part of the peak of the crystallization exotherm during cooling under strict observation conditions. The horizontal axis of the baseline and the peak of the crystallization exotherm are determined by the curve obtained from differential microcalorimetry analysis of the sample under study. These measurements are performed on samples that have been subjected to both rising and falling temperature changes of 10° C./Min.

The improvement in crystallization of the compositions according to the invention can be evaluated by a decrease in Δ compared to the coefficient Δ of the polyamide matrix or by an increase in Tgα, which characterizes the acceleration of crystal growth.

8 Glass Transition Temperature The glass transition temperature corresponds to a sharp decrease in shear modulus as a function of temperature.

This can be determined from graphs showing the changes in torsional modulus as a function of temperature, and these changes are measured by thermomechanical analysis using an automatic torsion pendulum. ] Ratio of amide groups per 100 molecular weight of polyamide polymer 1
A method for calculating the ratio (content) of amide groups per 100 molecular weight of a polyamide polymer will be shown, taking as an example a nylon-66 polymer obtained from the condensation of 1 mole of adipic acid and 1 mole of hexamethylene diamine.

This polymer has the following repeating unit and there are two NHCO groups within it. That is, the molecular weight of the repeating unit of the nylon-6 saccharide is 226 (the molecular weight of adipic acid is 146 +
There are two NHCQ molecules in the molecular weight of hexamethylene diamine (116) and the molecular weight of 2 moles of water removed during condensation (36 = 226).

Therefore, the number of amide groups per 100 molecular weight of the polymer is calculated as follows. Properties of the two matrices used in the following examples: Polyhexamethylene adipamide Example 1 Preparation of polycondensates with a low proportion of amide groups for the reinforcing phase 1 Dimer acids and Preparation of polyamide with hexamethylene diamine (polymer 1) 1.1 Preparation of the stoichiometric mixture of dimer acid and hexamethylene diamine A propeller stirrer is installed, which can be operated under a nitrogen atmosphere and the sample is taken from the bottom. The following was introduced into a 3e(7)1 reactor fitted with a 500 ml drop tube and a stopcock for sampling: 0.0
A fatty acid dimer having a monomer content of 1% by weight, a dimer content of 96.9% by weight and a trimer content of 3% (commercially available under the name Empol 1010 by Unilever Emery) In the above 2 Empol 1010″″, 96
．． 97% by weight of the dimer exists in the form of a mixture of isomers having essentially 3 carbon atoms, and the predominant isomer has the following structural formula.

The mixture was homogenized and the free space of the reactor was purged with nitrogen.

100 y of pure hexamethylene diamine, previously dissolved in 300 y of softened water, was then uniformly flowed into the stirred mass over a period of about 1 hour. The resulting clear solution was homogenized in three parts.

A small sample of approximately 1 g was taken and diluted with a water/isopropanol mixture (50/50 by weight) to give a salt concentration of 10%.

The pH value of this diluted solution was lower than the pH value at the equivalence point. Water/isopropanol mixture (50/50 by weight)
1.6f of a 50% strength solution of hexamethylene diamine in
into a concentrated solution.

This solution was homogenized for 30 minutes, and then the pH of the diluted solution was further measured. The PH value of the diluted solution is from the PH value at the equivalence point (8.67) to ±5/1 of the PH unit.
Reached within the range of 00. A stoichiometric solution of dimer acid and hexamethylene diamine was thus obtained. ．． 2 Preparation of polyamide A theoretical solution of dimer acid and hexamethylene diamine 80
0y to 1e equipped with a stirring system (scraping anchor stirrer rotating at 10-50 rpm) and a distillation column (height 40 cm 1 internal diameter 2.5C77!, multi-knit backing) and equipment allowing purging and cleaning with nitrogen. introduced into an autoclave.

The autoclave was purged three times with nitrogen at a pressure of 6 bar and then reduced to atmospheric pressure. The material was then slowly heated while stirring (50 rpm) with a slow nitrogen flow.

By raising the temperature of the material from 90°C to 180°C, the solvent was uniformly distilled over 9 drops. This material was then heated to 270°C for 1 hour. Stir for 10r
'Pm and the material was held at 270°C for 2 hours. 2
The material was continuously stirred at 700C and then mixed with 4 powders for 10 minutes.
It was placed under a vacuum of Tr$LHg and this vacuum was maintained for 3 minutes.

Stirring was stopped, the vacuum was released under nitrogen and the polymer was extruded from the autoclave under nitrogen at a pressure of 5 bar into a water-cooled trough. The resulting polymer, which is transparent and very slightly yellow, had the following properties: EHO. ? ml at °C
Blue elastic modulus: 18 DaN/d Proportion of amide groups per 100 molecular weight of polymer: Example 2 Production of polyamide of dodecamethylene diamine and dimer acid 2.1 Theoretical amounts of dimer acid and dodecamethylene diamine Preparation of the mixture The equipment described in Example 1 was used.

The following was introduced into the reactor: The dimer acid and a 50/5 solution of water and isopropanol were charged into the reactor and the mixture was homogenized by stirring under nitrogen.

Dodecamethylene diamine was added in portions over 1 hour with stirring. After the addition of the solution was completed, stirring was continued for 3 increments, so that the solution became completely clear and homogeneous. about 10
c! Take a sample of 50 l of water and isopropanol.
/5 dilution mixture to give a salt concentration of 10%.

The pH value of this solution was greater than corresponding to the equivalence point. Then 5.7y of Empol 1010 dispersed in water/isopropanol (5.7y) was added and the solution was homogenized again in three parts. Further P in dilute solution
H measurement was carried out. The pH value of the diluted solution is the equivalence point (8.
The pH value of 54) was within the range of ±0.05 of the PH unit. A stoichiometric solution of Enpol 1010 and dodecamethylene diamine was thus obtained. 2.2 Polyamide Production The apparatus described in Example 1 was used.

80 stoichiometric solution of dimer acid and dodecamethylene diamine
0y was placed in an autoclave.

The procedure described in section 1.2 above was then followed. The resulting polymer was transparent and slightly yellow and had the following properties: Mp by differential microcalorimetry: 86°C Torsional modulus at 20°C: 8.5 DaN/i Amide per 100 molecular weight of the polymer Proportion of groups: 0.27 Example 3 Preparation and properties of polyamide of 1,10-diamino-4,7-dioxadecane and dimer acid 3.1 Theory of dimer acid and 1,10-diamino-4,7-dioxadecane Preparation of a mixture The following was introduced into a reactor using the equipment described in Example 1: The dimer acid and a 50/5 solution of water and isopropanol were placed in the reactor and the mixture was purged with nitrogen. Homogenized by stirring at the bottom.

176f of 1,10-diamino-4,7-dioxadecane was added over 1 hour.

After the addition was complete, the mixture was stirred two more times. Approximately 1 ml of sample was then taken and diluted with a 50/5 mixture of water and isopropanol to give a salt concentration of 10%. The pH value of this solution was greater than that corresponding to the equivalence point.
Then a 50/50 mixture of water and isopropanol 3
3y of Empol 1010 dispersed in g.g.
The solution was again homogenized three times. The pH of a diluted solution with a concentration of 10% is tested, and the pH value of this solution is at the equivalence point (8
．． 61) within the range of ±0.05 of the PH unit.

A stoichiometric solution of dimer acid and 1,10-diamino-4,7-dioxadecane was thus obtained. 3.2 Polyamide Production The equipment described in Example 1 was used.

A stoichiometric solution of 820f of dimer acid and 1,10-diamino-4,7-dioxadecane was introduced into the autoclave.

The procedure described in section 1.2 was then followed. The resulting polymer was transparent and slightly yellow and had the following properties:
NII2 groups 19.80 Intrinsic viscosity: 0.512 d'/Fl Torsional modulus at 20°C 1.4 DaN/Ratio of amide groups per 100 molecular weight of TlrA polymer: 0.28 Example 4 Dimeric diamine and dimer The reaction was carried out in a stirred Pyrex reactor equipped with a nitrogen circulation system.

20 Da of a dimeric diamine having an amine number of 195-205 and an iodide value of 10-20 (Versamine 52 from General Mills Chemical Co.) and a dimer acid (Empol 1010).
)20.60y were introduced at ambient temperature. the mixture,
Stirred at ambient temperature under nitrogen.

The temperature was increased to 270°C over 1 hour and maintained at this temperature with stirring for 1 hour. Thus, at the end of the reaction a material with high viscosity was obtained and a very slight yellow coloration was observed. The polymer had the following properties: Sensitive Mp as determined by differential microcalorimetry: None Tg as determined by differential microcalorimetry: -300C Intrinsic viscosity: 0.55 d
'/y Ratio of amide groups per 100 molecular weight of polymer: 0.18
2 The elastic modulus of this product was approximately equal to that of the previous polyamide.

Example 5 Preparation and Properties of Polyamide from Hexamethylene Diamine (HrO), Bishexamethylene Triamine (BHMTA) and Dimer Acid The reaction was carried out in a 1e glass reactor equipped with a stainless steel anchor stirrer.

Equipment was provided for operation under nitrogen flow. Heating was ensured by immersion in a temperature controlled oil bath. Copolyamides containing 5 weight percent each of the following two polyamides were prepared: hexamethylene diamine/dimer acid and BHMTA/
Dimer acid.

577.6f dimer acid purified by distillation and 61.
87y of hexamethylene diamine and 102.17y of bishexamethylene triamine were charged into the reactor. The reactor was purged under nitrogen and immersed in a 90°C bath. The mixture was stirred and the temperature was increased to 200°C over 1 hour. This was kept at 200°C under stirring for 3 hours. The resulting polymer was extracted under slight nitrogen pressure. It was very slightly yellow in color and had the following properties: Tg by thermomechanical analysis: -14°C Intrinsic viscosity: 0.833 de/y Proportion of amide groups per 100 polymer molecular weight: 0.285
Torsional modulus at 20° C.: 32 DaN/d When heated to 260° C. on a hot plate or in a stirred reactor, the polymer crosslinked on itself within a few minutes to form an infusible compound.

The preparation of this polyamide makes it possible to determine the properties of the polyamide to be used as reinforcing phase in Example 9.

Example 6 Preparation of mixed phase polyamides based on hexamethylene diamine and dimer acids and copolymers of ethylene and acrylic derivatives A polyamide obtained from hexamethylene diamine and dimer acids according to Example 1; 50/5 copolymer obtained from ethylene, methacrylic acid and methacrylic ester (commercially available as Lupolene A291OMX)
The weighing mixture was prepared using a single screw extruder (screw diameter D: 25W1E1 length 20D) equipped with a proportional pump.

The reaction was carried out at 175-180°C. The mixture extruded into rods was extremely flexible and elastic and turned white upon stretching. The ratio of amide groups per 100 molecular weight of the polymer is 0
．． It was 1 Seki.

Example 7 A mixture consisting of 8 parts of polyhexamethylene adipamide (used as matrix) as described above and 2 parts of polyamide with carboxyl end groups obtained according to Example 1 was rotated and reciprocated. It was introduced into an apparatus containing a kinematically driven screw of the BUSS type and heated to a temperature of 280°C.

The output of the equipment was 8k9/Hr and the residence time of the polymer mixture was approximately 3-4 minutes.

This resulted in a polymer mixture whose Charpy notch impact strength was measured.

0.95J/c! The strength of i is measured and compared to
Polyamide alone used as matrix was 0.5
A significant improvement was observed with a Charpy notch impact strength of 6 J/cl$.

Example 8 A mixture consisting of 8 parts of polyhexamethylene adipamide (used as matrix) as described above and 2 parts of polyamide with carboxyl end groups obtained according to Example 4 was rotated and reciprocated. BUSS driven by motion
It was introduced into an apparatus containing a mold screw and heated to a temperature of 280°C.

The output of the equipment was 8k9/Hr and the residence time of the polymer mixture was approximately 3-4 minutes.

The resulting composition had improved properties primarily regarding Charpy notch impact strength.

Example 9 The procedure set forth in Example 8 was followed, but using the polyamide mixture section prepared in Example 5.

The composition had the following properties: Δ=33°C, Tgα=8\
Particle size 0.1-1μ. Example 10 Consisting of 8 parts by volume of polyhexamethylene adipamide (used as matrix) as described above and 2 parts by volume of a mixture of polyamide and a copolymer of ethylene and acrylic derivatives as described in Example 6 The mixture is placed in a single screw extruder, which has a screw diameter D of 25TI0f1 and a length of 20D and is heated to 275° C. with a proportional pump.

The mixture was extruded into rods and then converted into granules.

The product obtained under these conditions was dense, in contrast to a copolymer of polyhexamethylene adipamide (8 parts) with ethylene and an acrylic derivative (2 parts) prepared under similar conditions. The mixture with the ethylenic copolymer turned into a rod-shaped mixture having more or less gas pores due to thermal decomposition of the ethylenic copolymer. The composition according to the invention had the following properties: Δ=35°C, Tgα=801 particle size 0.1-1μ
, Notch impact strength after being stabilized at 100°C for 1 hour: 1.406±0.06 J/Cl, and flexural modulus: 19
6.50 ± 3.220 DaN/i Examples 11 and 12 Polyamide 1 of polycaprolactam (matrix) 280 Da and the dimer acid prepared in Example 1, both of which ξ is also granular.
20I1 was introduced into a 1' capacity stainless steel autoclave at ambient temperature.

After purging the apparatus with nitrogen, the temperature of the material in the autoclave was increased to 20 Cf'C over three cycles. Continue heating and when the temperature reaches a minimum of 250°C, reduce stirring to 5r'P.
It started at m. Raise the temperature to 270℃ for 1 hour,
Stirring was continued for an additional 4 hours at 270°C. The molten mixture is then withdrawn under nitrogen pressure and is made into a diameter of approximately 2T1.
r! n rods were collected in water and converted into granules. When this mixture was examined by differential microcalorimetry, the composite material was found to have two crystalline melting points, characteristic of the starting components.

Furthermore, the mixture does not change significantly with homogenization time;
It was found that the temperature changed from 1C@ to 24 powders at a temperature of 270°C. Exactly the same experiment was repeated, but using polycaprolactam 360d and the polymer 40y prepared according to Example 1.

The properties of the resulting mixture are shown in the table below.

Example 13 According to the procedure given in Example 10, the prolactam (matrix) 600y and the polyamide 66.0y prepared according to Example 2.
6y was used.

After purging the apparatus with nitrogen, the temperature of the material was increased to 270° C. over 1 hour while stirring at 10 r″Pm. The mixture was then stirred at 270° C. for 3 hours, and the mixture was then stirred as described above. The mixture was examined by differential microcalorimetry and it was found that the two starting polyamides remained well individualized and the overall size of the dispersed particles is 0.1~
It was 1μ. The properties of the resulting mixture are shown in the table below. Examples 14-17 The following four examples were carried out according to the first variant of the process for preparing the compositions of the invention described herein.

The method consists in introducing a polyamide corresponding to a flexible dispersed phase into a prepolyamide. The prepolyamide used, with an intrinsic viscosity of the order of 0.9 to 0.95 de/y, corresponds to the product obtained at the end of depressurization in a customary cycle for the polycondensation of hexamethylene diamine adipate. 50% aqueous solution of hexamethylene diamine adipate and 10% aqueous solution of acetic acid about 1
．． 80 da was placed in a 1e stainless steel autoclave.

While stirring, the temperature of the substance was increased to 220°C, which was 1
8. It corresponded to the natural water vapor pressure of Bar. Next, add 1 portion of water
The temperature of the material rose to 260'C. The pressure was then gradually reduced over a period of 1 hour and 3 minutes while simultaneously increasing the temperature of the material to 275°C. The desired amount of high molecular weight selective polyamide was then introduced into the autoclave and stirring was continued at 260° C. for 1 hour to homogenize the mixture. The mixture was finally extracted under nitrogen pressure and poured into water. The properties of the mixture obtained are shown in the table below.

A significant reduction in supercooling (Δ) and an increase in Tgα will be observed compared to the polyhexamethylene diamine matrix.

In Example 14, 800y of a 50% strength aqueous solution of hexamethylene diamine adipate and 86y of the polyamide prepared according to Example 1 were introduced.

In Example 15, 800y of a 50% strength aqueous solution of hexamethylene diamine adipate and 38y of the polyamide prepared according to Example 1 were introduced. In Example 16, a 50% strength aqueous solution of hexamethylene diamine adipate is
0y and the polyamide 86y prepared according to Example 2 were introduced.

In Example 17, 800y of a 50% strength aqueous solution of hexamethylene diamine adipate and 86q of the polyamide prepared according to Example 3 were introduced.

Example 18 This is an example of the second variant of the method according to the invention.

A dimeric diamine (Versamine 52 from General Mills Chemical Company) having an amine number of 195 to 205 and an iodide number of 10 to 20 was prepared on the one hand by a substantially dimer acid sold under the name Empol 1010; (See example 1 above)
and the other is about 9% by weight of a trimer acid having about 54 carbon atoms and about 1
% dimeric acid (this product is marketed by Unilever Emery under the name Empol 1041). A salt was prepared. Dimeric diamine of 120.68V, trimer diacid of 21.14 da (Empol 1041), dimer diacid of 10 & 17f (Empol 1010) and 250y perchlorethylene were mixed under nitrogen atmosphere. Equipment to operate it was installed and it was being stirred.11
was introduced into the reactor.

The mixture was left at ambient temperature for 1 hour with stirring.
The reactants became homogeneous very quickly after the reactants were introduced. Polycondensation of this salt was then carried out in the presence of hexamethylene diamine adipate.

393 q of dry hexamethylene diamine adipate, 200 y of distilled water, 169.5 q of a 50% strength solution in perchlorethylene of the salt prepared above, 0.18 y of acetic acid and approx. 1m1 and
It was introduced into a 1e stainless steel autoclave equipped to operate under pressure.

After several purges with nitrogen under pressure, perchlorethylene was distilled under atmospheric pressure by starting stirring and increasing the temperature of the reaction to 175°C.

Distillation was then stopped and the mixture was heated to 235°C. The autogenous water vapor pressure reached 1&/cool. Then, under this pressure, water vapor was further distilled by increasing the temperature to 260°C. Next, depressurize for 9 minutes,
The temperature was increased to 275°C. The reaction was completed by heating at 275° C. under nitrogen flow.

The composition thus obtained was extruded into water under nitrogen pressure and converted into granules.

The composition obtained had the following properties: Example 19 An example of the last variant of the process according to the invention was carried out by carrying out the polycondensation of prolactam containing the polyamide obtained according to Example 1 in solution with aminocaproic acid. This is demonstrated by conducting the test in the presence of

The reaction was carried out in a stirred 100c71 glass reactor equipped to operate under reduced pressure and heated by a temperature controlled alloy bath.

Polyamide (η) according to Example 1 with a prolactam of 201 and 5q.

=0.864) and 3y 6-aminohexane-1 acid were charged into the reactor at ambient temperature. After purging with nitrogen several times, the reactor was immersed in a heating bath controlled at 140'C. Stir the mixture. and increased the temperature. about 18
At 0°C, the material became homogeneous due to dissolution of the polyamide in the prolactam and its oligomers. The temperature continued to rise uniformly. At about 210°C, it was observed that the reaction became heterogeneous. After a reaction time of 2 hours, the temperature reached 270°C.

The material thus became heterogeneous and cloudy, and its viscosity increased rapidly. The temperature was maintained at 270°C for 1 hour, and then 1T1r of mercury was heated for about 3 minutes to remove free, unreacted prolactam. A vacuum of n was established. The mixture was kept under vacuum at 270°C for two periods. The polymer obtained at the end of the reaction was cloudy and had the following characteristics: This result shows that the polyamide produced according to Example 1 does not undergo any appreciable chemical interaction between the polyamides used. The results show that it is completely dispersed in polycaprolactam.

Example 20 Preparation of a copolyamide of adipic acid and hexamethylene diamine from 1 dimer acid A 1' autoclave (same as described in Example 1, 1.2) equipped with a stirring system was equipped with: I entered.

800y50% of a stoichiometric solution of dimer acid (Mbol 1010) and hexamethylene diamine prepared to 50% strength in a water/isopropanol mixture (50/50 by weight) as described in Example 1, 1.1. neutral salt solution
A 70y polymerization was carried out by operating as in Example 1, 1.2.

The almost colorless and transparent polymer obtained exhibited the following properties. 2 Preparation of a mixed phase from the aforementioned reinforcing phase and a matrix consisting of a copolyamide of adipic acid, hexamethylene diamine and prolactam.A mixture of hexamethylene diamine adipate and prolactam (90% by weight)
A copolyamide obtained by the polycondensation of 10) and exhibiting the following properties was used.

Amide group content per 100 molecular weight of polymer: 0.8
A composition according to the present invention was made by extruding a mixture consisting of a portion of dry granules (by weight b) selected as the matrix and a portion of the polymer granules selected as the reinforcing phase.

Extrusion was carried out by a single screw extruder with a screw diameter D of 20 mm and a length of 2 D, equipped with a proportional pump and with four single heating zones.

The extrusion conditions for the composition are summarized in Table 1 below.

The composition was extruded into rods and then granulated. The mechanical properties 1 measured for the injection molded test pieces are shown in the table below.
To summarize. Example 21 Preparation of copolyether amide of 1 dimer acid, polyoxypropylene diamine and prolactam
2. A 1e autoclave (same as described in Example 1, 1.2) equipped with a stirring system was charged with:

Prolactam 175f is commercially available from Texaco under the trade name 2-diefamine D2OOO'''', and has a molecular weight of 0.0968 per 100 molecular weight of the polymer. Polyoxypropylene diamine with an NH2 group content of
304.5y Dimer acid "Empol 1010" exhibiting the same set of properties used in Example 1, 1.2
84.8y.

Product name 2 Irganox 1010″ from Ciba Geigy
Antioxidant 2.5y ion exchange water commercially available as
The 200f autoclave was purged three times with 6 bar of nitrogen pressure and released to atmospheric pressure. Then the whole thing. Heating was carried out under atmospheric pressure and gradually brought to 150° C. over 90 minutes with stirring. The temperature of the contents was then gradually increased to 235° C. for 9 minutes under atmospheric pressure. Next, the whole was stirred at 235° C. and the pressure was gradually increased to 5 TWLHg with 4 powders. The whole is heated to 235℃ 5w0
Hold at nHg for 60 minutes. 47y during the reaction under reduced pressure
The prolactam was recovered by distillation. Stirring is stopped and the polymer is removed under a nitrogen pressure of 1.5 bar. The removed polymer was cooled by passing it through a cold water bath and then granulated.
The resulting nearly colorless, transparent, low viscosity polymer in the melt exhibited the following properties:

2 Preparation of a composition according to the invention from a reinforcing phase as described above and a matrix consisting of polycaprolactam (matrix B mentioned at the beginning of each example) The procedure was carried out as indicated in Example 20.2.

Tables 1 and 2 below show the extrusion conditions and the properties of the resulting mixed phase. Example 22 Preparation of a copolyether amide of 1 dimer acid, polyoxypropylene diamine and lauryllactam A 1e autoclave (same as described in Example 1, 1.2) equipped with a mixing system was equipped with: I entered.

It is commercially available from Texaco under the trade name "Diefamine D2OOO", and has a molecular weight of 0.0968 per 100 molecular weight of the polymer.
A polyoxypropylene lentiba with a content of 5 NH2 groups is an antioxidant commercially available from Geigy under the trade name 2 Irganoxus 1010''.A 2.5 q autoclave was purged three times with a nitrogen pressure of 6 bar and allowed to loosen to atmospheric pressure. Ta.

The entire contents were heated to 150° C. for 3 minutes under atmospheric pressure.
Purge once with 6 bar of nitrogen, release to atmospheric pressure and start stirring (50 r'Pm).

The whole was gradually brought to 275°C at 150°C under atmospheric pressure and then held at 275°C under atmospheric pressure for 6 minutes. Next, stir the whole thing at 275℃ and mix it by 3 times. The pressure was set to Hg. The whole at 275℃ 5? The mixture was continuously stirred under Hg pressure. 150 g of lauryllactam were distilled off during the reaction under reduced pressure. Stirring was stopped and the polymer was removed under a nitrogen pressure of 1 bar.

The highly fluid polymer removed was cooled by passing it through a cold water bath and then granulated. The resulting highly flexible, almost colorless, transparent, melt-state, low-viscosity polymer exhibited the following properties:

Content of amide groups per 100 molecular weight of the polymer 2 Preparation of the composition according to the invention from the reinforcing phase described above and a matrix consisting of polyundecaneamide B Polyundecaneamide, which exhibits the following characteristics, was used.

The composition was made as shown in Example 20-2! -2) and (2) show the extrusion conditions and properties of the obtained mixed phase.

Example 23 Preparation of copolyether amide of 1 dodecanedioic acid, polyoxypropylene diamine and prolactam In a 1' autoclave (same as described in Example 1, !1.2) equipped with a stirring system, the following were added. I loaded it.

It is commercially available from Texaco under the trade name 2-diefamine D2OOO'''', and has a molecular weight of 0.0968 per 100 molecular weight of the polymer.
The polyoxypropylene polycondensation showing a content of 5-NH2 groups was carried out in an analogous manner as described in Example 21, 1. During the reaction under reduced pressure, 25y of prolactam was recovered by distillation. Ta.

The resulting almost colorless, transparent, low viscosity polymer in the melt had the following properties:

2 Production of the composition according to the invention from the reinforcing phase described above and a matrix consisting of polyhexamethylene azelamide
Polyhexamethylene azeramide, which is commercially available from Monsanto Company as 2vidyne 60H''5 and exhibits the following properties, was used.

η, Nh = 1.406C1e/da [measured in a formic acid/water mixture (90/10 by volume) instead of m-cresol]
The composition was prepared as shown in Example 20.2.

Tables (1) and (2) show the extrusion conditions and the properties of the resulting mixed phase. Example 24 A composition according to the invention was prepared as shown in Example 20.2 from a reinforcing phase as described in Example 2 and a matrix consisting of a copolyamide of adipic acid, isophthalic acid and hexamethylene diamine.

The matrix used here was manufactured as follows.
A 1e autoclave (same as described in Example 1, 1.2) equipped with a stirring system was charged with:

The whole was heated to 80° C. and the autoclave was purged three times with 5 bar nitrogen pressure and allowed to relax to atmospheric pressure.

The inlet of the autoclave was then closed and the entire contents were brought to 210° C. for 3 minutes with stirring. The pressure obtained was 18/\bar. The temperature of the contents was increased by 9 degrees to 260 C and the water was distilled under a pressure of 1 sig. Reduce stirring to 10 r'Pm and reduce overall temperature to 285
Distillation of water was continued while gradually increasing the pressure to 9°C while gradually lowering the pressure. The polymer was homogenized in three batches at 285° C. under atmospheric pressure with strong agitation (10 r'Pm).

Stirring was stopped and the polymer was removed under 10/cool nitrogen pressure. The removed polymer was cooled by passing through a cold water bath and then granulated. The obtained polymer exhibited high viscosity in the molten state.

Claims (1)

[Claims] 1 (i) prepared by condensing a saturated dicarboxylic acid having 4 to 12 carbon atoms with a diamine having 4 to 14 carbon atoms, or from these saturated dicarboxylic acids; produced by ring opening of a derivatized lactam;
or a matrix-forming phase 55 which is a nylon polyamide resin having a number average molecular weight of at least 5000 prepared by copolymerizing at least two of the above monomers with or without isophthalic acid. ~99% by weight and (ii) at least 500%
Particles in the range from 0.01 to 10μ of a polyamide having a molecular weight of 0, a content of amide groups in a proportion that is less than 40% of the amide groups of the matrix-forming polyamide resin, and a glass transition temperature of less than 5°C. 1 to 45% by weight of a particulate dispersed phase having the following dimensions: (a) (a1) obtained by dimerizing a fatty acid having 16 to 26 carbon atoms; (a2) combination of such fatty acid dimer or derivative thereof with an aliphatic diacid or lactam having 12 or less carbon atoms, or 16 to 26 carbon atoms; Acid components and acid compounds consisting of mixtures with trimers of fatty acids having atoms, or (a3) aliphatic diacids mixed with lactam as an optional component correspond to (a1) and (a2) above. In the case of a primary diamine, or (b3) a mixture of an aliphatic di-primary diamine and a second di-primary aliphatic triamine as defined under (b1) above, or (b4) 16 to 26 If the dimeric diamine obtained from a dimer of a fatty acid having carbon atoms or the acid compound corresponds to (a3) above, (b5) a polyether diamine containing more than 18 carbon atoms; monodiamine, and the polyamide dispersed phase can further contain another polymer consisting of a copolymer of ethylene and an acrylic acid derivative. A thermally stable multiphase polyamide composition having improved mechanical properties.