CS257265B2 - Preparation method of block polyamide copolymere - Google Patents

Abstract

Process for preparing block polyamide of the copolymer which is carried out such that the epsilon-caprolactam compound is mixed containing N-acyl lactam functional groups selected from the group consisting of adducts polyethertriol of molecular weight 1,000 to 10,000, preferably 3,000 to 6,000 with an aliphatic or aromatic dihalide dicarboxylic acids and epsilon-caprolactam, at least one molecular amine weight of 60 to 10,000, preferably up to 6,000 selected from aliphatic monomeric polyamines and aliphatic polymeric polyamines with polyether or polyalkylenimine skeleton whose multifunctionality is consists of at least two primary and / or secondary amino groups, wherein the amount the multifunctional amine is at least 0.02 equivalent of the sum of primary and secondary amino groups based on the N-acyl lactam equivalent groups contained in the compound, and a catalyst for anionic lactam polymerization, the mixing being carried out by mixing first, a compound with N-acyl lactam groups with part of caprolactam and amine and a catalyst with caprolactam residue the two premixes are then mixed together

Description

The invention relates to a process for the preparation of high impact strength polyamide materials consisting of block copolymers comprising polyamide and elastomeric segments. In particular, the invention relates to a process for preparing crosslinked block polyamide copolymers.

Block polyamide copolymers may generally consist of alternating blocks of polyamide segments, such as segments of elastomeric polymers such as polyether, polyester, hydrocarbon, or polysiloxane residues. Block polyamide copolymers are generally produced by copolymerizing lactam monomer and elastomeric polymers and may be linear or branched depending on the structure of the elastomeric polymer used. A more detailed evaluation of the structure and methods of making the type of block polyamide copolymer is given in U.S. Patent No. 4,031,164 to Hendrick and Gabbert.

The properties of the polyamide segments and segments of the elastomeric polymers contained in the block copolymers affect, as stated in the above-mentioned Hendrick and Gabbert patent, the properties of the resulting polymer. In order to obtain a material with a high modulus of elasticity, it is necessary to use polyamide segments of higher molecular weight and / or higher percentage by weight. Higher ductility and better impact properties can be achieved in the manufacture of block polyamide copolymers using higher weight content and / or higher molecular weight elastomeric polymers.

Influencing the properties of the block polyamide copolymers in other ways would be advantageous.

The present invention relates to the crosslinking of block polyamide copolymers using multi-functional amines.

Crosslinked block polyamide copolymers according to the present invention are obtained by a reaction process in which the block polyamide copolymers are crosslinked by the action of multifunctional amines.

This may be accomplished, for example, by reaction between acyl lactam functional compounds and multifunctional amines to provide a cross-linked acyl lactam functional group which subsequently or simultaneously reacts with the lactam monomer in the presence of an anionic lactam polymerization catalyst to form cross-linked block polyamide copolymers. The properties of the resulting block copolymers may vary depending on the degree of crosslinking.

In particular, block polyamide copolymers consist of alternating blocks of polyamide segments of the formula

Wherein X represents a 1,5-pentylene group and m is an integer greater than one, and segments of polyether elastomeric polymers. A more detailed description of such a block polyamide copolymer is given in U.S. Patent No. 4,031,164.

There are a number of methods for producing block polyamide copolymers. One general method is to use polyether elastomeric prepolymers that provide elastomeric segments in block polyamide copolymers and monomeric caprolactam. The elastomeric prepolymer is prepared so as to contain a lactam initiating group by which it polymerizes further caprolactam to form polyamide segments. The lactam initiating group is an acyl lactam group which is a known initiator of lactam polymerization.

The use of elastomeric polymers containing acyl lactam groups for the production of block polyamide copolymers is described in European Patent Application No. 67,695. The above-mentioned acyl lactam functional compounds can then be reacted with epsilon 3.

-caprolactam in the presence of a basic polymerization catalyst of kaltam to form block polyamide copolymers.

As noted above, block polyamide copolymers exhibit the properties afforded by segments of elastomeric polymers and polyamide segments.

In the process according to the invention, when crosslinking block polyamide copolymers with multifunctional amines, the overall properties of the resulting polymer can be varied while maintaining a constant molecular weight and a constant weight content of elastomeric polymers. Said cross-linking is achieved by reaction between the at least one compound with N-aeyllactam functional groups and the at least one multifunctional amine and subsequent or simultaneous reaction with epsilon-caprolactam in the presence of an anionic polymerization catalyst of the lactams.

SUMMARY OF THE INVENTION The present invention provides a process for preparing block polyamide copolymers comprising mixing epsilon-caprolactam, a compound containing N-acyl lactam functional groups selected from the group consisting of polyethertriol adducts having a molecular weight of from 1,000 to 10,000, preferably from 3,000 to 6,000, with an aliphatic or aromatic dicarboxylic acid dihalide and epsilon-caprolactam, at least one multifunctional amine having a molecular weight of 60 to 10,000, preferably up to 6,000, selected from the group consisting of aliphatic monomeric polyamines and aliphatic polymeric polyamines with polyether or polyalkylenimine backbones. consisting of at least two primary and / or secondary amino groups, wherein the amount of the multifunctional amine is at least 0.02 equivalent of the sum of primary and secondary amino groups, based on the equivalent of N-acyllactam groups, and the anionic polymerization lactam catalyst The mixing is carried out by mixing the compound having the N-acyl lactam groups with a portion of caprolactam and the amine and the catalyst with the remainder of the caprolactam, and then mixing the two premixes together.

The multifunctional amines used in the process of the invention preferably contain at least three primary or secondary amino groups. These are compounds which may have different molecular weights and different structures. All polyfunctional amines as defined above which are capable of cross-linking acyl-lactam-functional compounds and / or block polyamide copolymers are suitable for the process of the invention. The amine function may be located at the end of the organic compound, may be bound in the side chain, or may be inside the organic compound, as in the case where an amino group connects two chains. The multifunctional amine must contain at least two primary or secondary amine functional groups. Tertiary amines are not reactive with the acyl lactam functional groups of the N-acyl lactam-containing compound and therefore do not cause crosslinking of the block polyamide copolymers of the present invention. However, it is known in the art that typical commercial mixtures of multifunctional amines may contain a range of multifunctional mines composed of primary, secondary and tertiary amines. A composition of this type will be useful in the practice of the present invention if a sufficient amount of multifunctional amines carry at least two, and more preferably at least three, primary or secondary amine groups that will react with acyllactam functional groups thereby causing crosslinking of acyllactam functional groups and ultimately block polyamide copolymers.

As mentioned above, different types of multifunctional amines of different molecular weights can be used in the process of the invention as long as they are capable of crosslinking acyl lactam functional compounds and / or block polyamide copolymers. The type of multifunctional amine used may affect the physical properties of the block polyamide copolymers prepared therefrom. Preferred multifunctional amines are polyamines having a polyether or polyethyleneimine backbone. The molecular weight of the polyamines is preferably at least 500. The term molecular weight used in the specification and in the following examples refers to the number average molecular weight as determined by the prior art φ. Particularly preferred polyfunctional amines are polyoxyalkylene polyamines in which alkylene the group contains 2 to 4 carbon atoms, having a molecular weight in the range of 400 to 5,000. The most preferred multifunctional amines are polyamines which are generally prepared by polymerizing alkylenimines such as ethylenimine and by polymerizing organic diamines such as alkylenediamines resulting in interchain-containing polyamines. secondary and tertiary amino groups.

These preferred polyamines have molecular weights ranging from 60 to 10,000. Examples of such polyamines are polyethylanimines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and triethylediamine. Polyether amines can be prepared from polymers containing functional groups reactive to di- or polyfunctional amine monomers, so that the corresponding multifunctional amines are formed by the appropriate reaction. Reductive amination of polyols, cyanoethylation of polyols followed by hydrogenation or reaction of 2 equivalents of diisocyanate with all hydroxyl groups of the polyols and reaction with water can be obtained. Other methods for preparing these multifunctional amines are known in the art.

The use of polyetheramines or other polyamines having a glass transition temperature below 20 ° C can have a significant effect on the ductility and impact properties of the block polyamide copolymers prepared therefrom, especially if the polyamine has a relatively high molecular weight.

The effect on these properties can be so great that the molar ratio of N-aoyllactam functional compounds to polyamines can be reduced without affecting the overall properties that are determined by segments of the elastomeric polymer of acyllactam functional compounds.

The term N-acyl-lactam functionality refers to a carboxylic acid derivative and epsilon-caprolactam. The term N-acyl lactam functionality refers to the number of acyl lactam groups per molecule of compound having N-acyl lactam functional groups. These acyl-lactam-functional compounds can be produced by any of the prior art methods. The compound containing the N-aryl lactam functionality must be formed from a polyether elastomer such that the resulting block polyamide copolymer has a recovery value after tensile deformation of at least 50 percent. The tensile recovery is determined on a dry molded polymer sample that has been stretched 50% of its original length (1) and held in this condition for ten minutes before the stress was released. Ten minutes after the voltage is released, the length (l _r ) of the sample is measured. Tensile recovery is

1.5 1 - 1L

--— x 100.

0,5 1

In order for the elastomeric polymer to provide the above tensile recovery, it is usually required that the block polyamide copolymer contain at least 50% by weight of the elastomer. However, the amount of elastomeric polymer in the block polyamide copolymers of the invention is not limited to at least 50% by weight, since both lower and higher proportions in the range of 10 to 90% by weight also provide improved polyamide polymers.

As already mentioned, the compound having N-acyl lactam functionalities is derived from elastomeric polyethertriols having a molecular weight of 1,000 to 10,000, preferably 3,000 to 6,000.

One preferred compound having N-acyl lactam functional groups has the following general formula:

Z - / 0 - A (Q) _b / _n in which

Q is the rest of epsilon-caprolactam,

Z is a segment of a polyether elastomeric polymer as defined above;

A represents a group of formula

O

AND

C - or

or a mixture thereof and preferably a group of formula - c - R 4 c b represents an integer equal to 1, 2 or 3;

R represents a hydrocarbon group and n is an integer greater than 1, preferably greater than 2 and more preferably equal to 3.

Compounds with N-acyl lactam functional groups are prepared by reacting the above-defined polyether trioles with aliphatic or aromatic-type dicarboxylic acid dihalides such as terephthalic or isophthalic acid halide (where R is phenylene) in the presence of an acid acceptor and subsequent reaction with epsilon-caprolactam.

The crosslinked block polyamide copolymers of the present invention are prepared under conditions such that polyfunctional amines are reacted with the acyl lactam groups of the compounds with N-acyl lactam functional groups prior to or simultaneously with the polymerization of caprolactam. This results in crosslinking of compounds with N-acyl lactam functional groups which, after subsequent or simultaneous polymerization of caprolactam, provide cross-linked block polyamide copolymers. One particular type of compound having an N-acyl lactam function and / or one type of a multifunctional amine, or a mixture of the above-described compounds having an N-acyl lactam function and / or a mixture of multi-blowing amines may be used in the process of the invention.

The resulting block polyamide copolymer will typically contain at least 10% by weight of caprolactam block polymer, preferably from 10 to 90% by weight and more preferably from 60 to 80% by weight.

The reaction between a compound with N-acyl lactam functionality and a multifunctional amine is usually carried out in the presence of caprolactam and a catalyst. The reaction conditions are chosen such that the reaction between the multifunctional amine and the acyl-lactam-functional compound prevails over the polymerization of caprolactam. This can be achieved by keeping the reaction temperature below the optimum temperature for lactam polymerization in the mixing step, for example by keeping the temperature below about 100 ° C and then raising the reaction temperature to values above about 100 ° C, for example in the range 110 to 150 ° C to promote the polymerization of caprolactam. In a preferred embodiment, the reaction conditions are chosen to allow simultaneous reaction, for example by raising the temperature to 130 to 150 ° C immediately after mixing the reactants.

The amount of multifunctional amine to be used in the process of the invention should be sufficient to improve tensile properties and / or tear strength of the block polyamide copolymers. The amount required will largely depend on the molecular weight and functionality of the polyamine, smaller amounts will be required at high molecular weight and high functionality. The polyamine is preferably present in an amount of at least 0.02 equivalents, more preferably at least 0.2 equivalents, and even more preferably 0.3 to 0.6 equivalents of amino groups (primary plus secondary) per equivalent of N-acyl lactam groups.

The resulting bond between the multifunctional amine and the N-acyllactam group of a compound having N-acyllactam functional groups is likely to be as follows:

⁰ 9, “*>

Elastomeric segment (vx NH-Y-C-X-C-Y-NH X) An elastomeric segment wherein X is a multifunctional amine moiety and the bond consists of the amine groups of the multifunctional amine and the carboxyl group of the lactam moiety. The multifunctional amine from which the X group is derived, as mentioned above, may have amino groups positioned at the end position of the polymer molecule, in the side chains of the polymer, or incorporated into the polymer as intrapolymer groups.

A typical lactam-functional block polyamide copolymer cross-linked which was made from a preferred compound with an N-acyl multifunctional amine has the following general formula:

I - {C-Y-NHt A-1H-Y-Ct 0 Z-O-f-Y-NHt

O

AT

-At NH-Y-Ct X • phe-Y-NHt -A ^m 4 (NH

-Y-go

0-Z

C-Y-NHt A (NH-Y-C + m ₆ m _?

-N 'wherein Z and A are as defined above,

X represents a radical of a multifunctional amine as defined above,

Y is a 1,5-pentylene group, p is an integer equal to or greater than 1 and preferably greater than 3, m, m ₃ , m ₂ , m 2, m 2, m 2, mg and m 2; are integers equal to one or greater, and n and n are integers equal to one or greater, preferably equal to two or greater, and more preferably equal to three or greater.

As can be seen from the above crosslinked block polyamide copolymer formula by reaction between an elastomeric segment with N-acyl lactam functionalities and a multifunctional amine, amide bonds are formed (λ ^ NH-Y-CO-X-CO-X-CO-Y-NHZVZ) between functionalized an elastomeric segment and a multifunctional amine.

Examples la2

The following examples demonstrate two methods of crosslinking elastomeric segments with N-acyl lactam functional groups. Example 1 shows the process of the present invention starting from the reaction of a polyol and a bisimide (or bis-acyllactam) to form elastomeric segments with acyllactam functional groups, which then eragate with a multifunctional amine and then with monomeric caprolactam. Example 2 demonstrates the process of the present invention starting from an elastomeric segment with N-acyl lactam functional groups, which is crosslinked with a multifunctional amine and subsequently reacted with caprolactam. The two examples 1 'and 2' were carried out in exactly the same procedure and from the same substances but without a multifunctional amine to compare properties between the crosslinked block polyamide copolymer of the invention and the block polyamide copolymer that did not undergo such crosslinking.

He did

117 grams (g) of ethylene oxide-terminated polyoxypropylene triol having a molecular weight (MW) of about 4800, 26.3 g of N-adipoyl-bis-caprolactam, 5 g of caprolactam and 1.5 g of Flectol H were charged to a 500 ml flask. (antioixdant). The mixture was heated and stirred under vacuum at 133 Pa at 125 ° C for 30 minutes and then cooled to 85 ° C.

In a second flask, 225 g of caprolactam was dried by heating under vacuum until 25 ml was distilled off. The caprolactam was then cooled to 75 ° C and 15 ml of 3 molar ethylmagnesium bromide in diethyl ether solution was added. This flask was evacuated to complete degassing and 3.7 g of polyoxypropylenediamine (approximate MW 230) was added.

The contents of both flasks were simultaneously injected into a two-piece closed mold lined with Teflon, which had been pre-heated to 130 ° C. The two mold parts were separated by a 3.2 mm Teflon liner. The components were injected into a mold through a Kenics static mixer, 6,35x152,4 mm using a Zenith no. 5 at 200 rpm ^- '''.

After five minutes, the castings were removed from the mold. The resulting block polyamide copolymer contained 40% polyether.

Example 2

The compound with N-acyl lactam functionalities was prepared by reaction of ethylene oxide-terminated polyoxypropylene triol (approx. 4800 MW), terephthalic acid chloride and excess caprolactam in tetrahydrofuran at 40 ° C in the presence of triethylamine (acting as an acid reporter). The molar ratio of triol to terephthalic acid chloride used to prepare this functional group was 2: 5.

A 500 ml flask was charged with 134 g of the above-described N-acyllactam functional compound and 43 g of caprolactam. The mixture was heated under vacuum at a heating temperature of 140 ° C until 25 ml of caprolactam was distilled off and then cooled to 85 ° C.

In a second flask, a 0.23 molar solution of bromoabnesiumprolactam was prepared by adding 15 ml of a 3 molar solution of ethylmagnesium bromide in diethyl ether to 200 g of dry caprolactam. Then 2.12 ml (2.0 g) of polyoxypropylenediamine (approximately MW 230) was added. 30% equivalent of the primary and secondary amino groups of the multifunctional amine were used compared to the equivalent of the N-acyl lactam groups of the compound containing the N-acyl lactam functional groups. The contents of both cells were injected into the mold as described in Example 1. After 5 minutes, a block polyamide copolymer containing 40% polyether was removed from the mold.

Comparative Examples 1 'and 2'

Two Comparative Examples 1 'and 2' were performed by the same procedure and using the same substances (without polyfunctional amine) as described above for the corresponding Examples 1 and 2.

For block polyamide copolymers produced in the form of castings according to Examples 1 and 2 and Comparative Examples 1 'and 2', various properties were tested, essentially according to the following methods:

Tensile strength: ASTM 638 / units are megapascals (MPa) /

Tear Strength: ASTM D1004 / units are Newtons per meter (N / m) /

Tensile modulus: ASTM D638 / units are megapascals (MPa) /

Ductility: ASTM D638 / units% /

The results obtained in Examples 1 and 2 and Comparative Examples 1 'and 2' are shown below in Table I. As can be seen from Table X, the properties of the block polyamide copolymers were generally improved by sieving. The only property that has been negatively affected by sieving is the flexural modulus. However, for certain applications, this reduction is not significant.

Table I

Tensile properties

Strength MPa Ductility % Recovery ⁴ % Bending module MPa Strength in tear N / m Comparative Example 1 ' 23,098 320 78 69,639 71 273,026 Example 1 23,167 370 78 55.160 72,673.97 Comparative Example 2 ' 24,615 320 - 115,146 73 549.56 Example 2 25,649 330 72 92,393 78 803.1

⁴ Recovery from tensile test was determined after breaking

Examples 3 to 9

Examples 3-9 demonstrate the use of di- and tri-functional amines for crosslinking block polyamide copolymers by the process of the invention.

A premix of the N-acyllactam functional compound solution was prepared by dispensing 1,800 g of the N-acyllactam functional elastomer segment prepared according to Example 2 into a flask together with 18 g of Flectol ODP antioxidant. The mixture was heated with vigorous stirring for 1 hour at 100 ° C under 1 mbar to remove any moisture. The mixture was then cooled to 75 ° C and divided into 200 g fractions for Examples 3 to 9.

A premix of a 0.18 molar solution of caprolactammagnesium bromide in caprolactam (catalytic solution) was prepared by adding 60 ml of 3 molar ethylmagnesium bromide in diethyl ether solution to 1000 g of molten dried caprolactam followed by complete degassing under a vacuum of 133 Pa. Various types of multifunctional amines were added to the catalyst solution in an amount

See Table II below. Table II Mixture Cat. solution / amine 3 Eq. amine (*) Example C. Used amine catalytic solution (G) Amin (G) 3 HMD ¹ 112.9 1.54 25 4 HMD 137.3 2.64 33 5 HMD 109.7 2.33 37.5 6 HMD 103.8 2.41 40 7 TAN ² 118.2 1.60 25 8 TAN 146.6 2.48 30 9 TAN 163.4 2.91 32

Hexane-1,6-diamine nonantriamine □

the percentage of amino group equivalents (total primary and secondary amino groups) relative to one equivalent of N-acyl lactam functional groups in each 200 g sample of the N-acyl lactam functional group.

-AND

The N-acyllactam functional compound solution and the multifunctional amine catalyst solution were pumped into a vertical two-piece teflon-lined mold and preheated to 130 ° C. The mold parts were separated by a 3.17 mm thick Teflon liner. Solutions were introduced into the mold through a Kenics static mixer, two milliamperes 6,35x152,4 mm Zenith gear pumps no. 5 at the speed of 200 min ^-1.

The proportions of the pumped components were 2.57 ml of N-acyllactam functional compound solution per ml of catalyst solution. In each example, the block polyamide copolymers cured to a hard resin within 30 to 60 seconds.

The resulting properties found in Examples 3 to 9 are shown below in Table III. These properties were determined as described in Examples 1 and 2.

Table III

Example Tensile strength Ductility Recovery C. MPa <%> in turn 3 8 480 300 92 4 8 756 383 86 5 11 859 407 90 6 10 894 449 88 7 7 515 317 88 8 8 136 472 85 9 6 550 364 88

⁺ Tensile recovery was determined after rupture

Examples 10 to 16

Examples 10 to 16 demonstrate the dependence of the properties of the amine crosslinked polyamide copolymers according to the invention on the different molar contents of diamines and triamines.

In each example, a premix of a solution of a compound having N-acyllactam functionality was used. This premix was prepared by dispensing 1,067 g of the N-acyllactam functional compound prepared according to Example 2, 158 g of caprolactam and 0.4 g of copper acetate, monohydrate into a 21 liter flask. The blend was dried by distilling 25 ml of the substance under vacuum at 140 ° C. The dried solution was maintained at 100 ° C under vacuum until use until the vacuum was released into nitrogen.

Single doses (200 g) of the catalyst solution were prepared for each of the examples.

Each of these batches of catalyst was prepared by dispensing 193 g of caprolactam plus a given type of amine into the 500 ml flask in the amounts listed in Table IV below. The catalyst solution was dried by distilling 25 ml of the substance under vacuum in an oil pump at 140 ° C. The temperature was adjusted to 125 ° C and 32 g of catalyst concentrate was dissolved in each batch. This catalyst concentrate contained 1.05 mol / kg of caprolactammagnesium bromide in caprolactam. Each of the prepared catalyst solutions contained 0.16 mol / kg caprolactammagneisumbromide. The catalyst solutions were kept at 100 ° C under vacuum until use was released under nitrogen. Table IV below lists the types and amounts of amines used and the mole percent of amino groups to acyl lactam groups.

and

Table IV

Example Amine used Amine Equivalents ³ (») g of amine 10 none 0 0 11 PEI-6 ² 30 1.17 12 PEI-6 60 2.24 13 PEI-6 90 3.41 14 PEI-6 150 5.66 15 Dec PEI-18 ³ 60 2.24 16 PEI-18 90 3.41

The amino group equivalent (sum of primary and secondary amino groups) for the N-acyllactam functionality of the compound with the N-acyllactam functionality at the ratio of the N-acyllactam functional compound solution to the catalyst solution of 1: 1.

PEI-6 = poles (ethyleneimine) having a molecular weight of 600. Of the amino groups, 25% are primary,% secondary and 25% tertiary.

PEI-18 = pply (ethyleneimine) with a molecular weight of 1,800. Distribution of amine groups as in PEI-6.

The N-acyllactam functional compound solution and the catalyst solution were simultaneously injected through a Kenics static mixer, 6.35 mm, into a 203x203x3.17 mm vertical mold that had been pre-heated to 130 ° C by two Zenith No. 5 gear pumps. at 200 rpm ³ . The resulting block polyamide copolymer castings contained 40% polyoxypropylene.

The above castings of Examples 10 to 16 were subjected to the property tests listed in Table 5 below according to the test methods of Examples 1 and 2 with another bending recovery test as follows:

Bending Recovery - Casting bent 180 ° through 12.6 mm mandrel for 30 seconds. Recovery values were determined after 5 minutes. The units are%.

The results of these tests are shown in Table 5 below.

Table V

C. Eq. amine % Tensile strength MPa Ductility % Modulus of elasticity in tension MPa in Strength retention N / m Recovery in bend% 10 0 33,440 340 374,399 113 826.7 79 11 30 39,370 400 499,198 140 094.4 73 12 60 40,474 380 521,262 145 347.94 73 13 90 35,440 320 462,654 134 840.86 74 14 150 36,199 330 331,649 134 840.86 73 15 Dec 60 38,956 350 523,330 141 845.58 72 16 90 37,646 340 484,718 136 592.04 73

Ductility, tensile strength, tensile modulus, and tear strength improved in the range of percent amino equivalent of from about 30 to about 60%. At a rise above 60%, the values of these properties deteriorated but were still better than in Example 10. The bending recovery with crosslinking deteriorates, but this property is not critical in certain applications. The overall property profile has improved.

Examples 17 to 20

Examples 17 to 20 demonstrate the properties of block polyamide copolymers cross-linked with a polyethertriamine according to the method of the invention, wherein the amount of the compound with N-acyl lactam functional groups was reduced according to the amount of polyethertriamine used. The parts of the polyetheramine obtained by elastomeric properties compensated for the reduced amount of compound and the acyl lactam N-functional groups used in the manufacture of the block polyamide copolymers.

The N-acyllactam functional compound was prepared as described in Example 2. For Examples 17-20, batches of the N-acyllactam functional compound were prepared in caprolactam solution. The corresponding amounts of the compound having N-acyl lactam functionalities and caprolactam that were used for the solution in each example are shown in Table VI below.

Table VI

Example Compound with N-acyl lactam Caprolactam ³ groups (g) (g)

17 132 43 18 124 51 19 Dec 131 44 20 May and) 120 55

¹ dose of 25 g of caprolactam involves extra distillation to dry the solution. The dose also includes 0.06% by weight of cupric acetate hydrate (antioxidant).

The catalyst solution in all these examples was prepared as described in Examples 10-16. Each solution contained a final concentration of 0.16 moles of caprolactammagnesium bromide per kg of caprolactam solution. A polyfunctional amine was added to the catalyst solution, with the type, amount and percentage of primary and secondary amino equivalents relative to the N-acyl lactam equivalent (amine equivalence) for each example given in Table VII below.

Table VII

Example g of caprolactam ³ Used amine Equivalence amine% g of amine g katal. concentrate 17 191 T-403 ² 20 May 1,8 32 18 185 T-403 100 ALIGN! 8.1 32 19 Dec 191 T-3000 ³ 4 2.5 32 20 May 176 T-3000 30 17.2 32

caprolactam includes 25 g additionally for distillation of polyoxypropylene triamine, approximate molecular weight 400 (Jeffamine T403) ³ polyoxypropylene triamine, approximate molecular weight 300 (Jeffamine T-3000).

In all examples, the properties listed in Table VIII were tested according to the test methods reported previously. The test results are summarized below for each of the examples together with the properties of Example 10, which are presented again for comparison.

Table VIII

Ex. Eq. amine % Tensile strength MPa Ductility % Modulus of elasticity in tension MPa Strength retention N / m Recovery in bend% 10 0 33,441 340 374,398 115 577.88 79 17 20 May 37,026 390 509,540 136 592.04 73 18 30 40,680 460 448,864 138 343.22 74 19 Dec 4 41.094 450 415,768 143 596.76 73 20 May 30 33,096 350 386,809 136 592.04 72

From the results shown in Table VIII, block polyamide copolymers which have been crosslinked show a significant improvement in properties. The above results also illustrate the significant improvement obtained using multifunctional amines when the functionality of the amine is at least three (based on primary and secondary amino groups).

Although preferred embodiments have been described in the above examples, modifications and changes thereof can be made without departing from the scope of the invention. Thus, the foregoing description is merely intended to illustrate the invention and not to limit it.

OBJECT OF THE INVENTION

Claims (4)

OBJECT OF THE INVENTION A process for the preparation of a block polyamide copolymer, comprising mixing epsilon-caprolactam (I), a compound (II) containing N-acyllactam functional groups selected from the group consisting of polyethertriol adducts having a molecular weight of 1,000 to 10,000, preferably 3 000 to 6000 with an aliphatic or aromatic dicarboxylic acid dihalide and epsilon-caprolactam, at least one multifunctional amine (III) having a molecular weight of 60 to 10,000, preferably up to 6,000, selected from the group consisting of aliphatic monomeric polyamines and aliphatic polymeric polyamines with polyether or a polyalkyleneimine backbone, the functional of which comprises at least two primary and / or secondary amino groups, wherein the amount of the multifunctional amine (III) is at least 0.02 equivalent to the sum of the primary and secondary amino groups; based on the equivalent of the N-acyllactam groups contained in compound (II), and the catalyst (IV) of the anionic polymerization of lactams, the mixing being carried out by mixing compound (II) with N-acyllactam groups with a portion of caprolactam (I) and the amine (III) and the catalyst (IV) with the remainder of caprolactam (I), whereupon the two masterbatches are mixed together. 2. A process according to claim 1, wherein at least 0.2, preferably 0.3 to 0.6 equivalents of the sum of the primary and secondary amino groups of the amine (III) is used per equivalent of the N-acyl lactam functional groups of compound (II). . 3. The process of claims 1 and 2, wherein the mixing of the masterbatch, wherein the compound (II) is reacted with the N-acyllactam groups with the multifunctional amine (III), is carried out at a temperature below 110 ° C. the reaction mixture is polymerized at 110-150 ° C. 4. The process according to claim 1, wherein the reaction of compound (II) with the N-acyl lactam groups with the multifunctional amine (III) and the polymerization of caprolactam (I) are carried out simultaneously, mixing the premix and maintaining the resulting reaction mixture at 130. to 150 ° C. Severography, n. P., MOST