JPH0363973B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the field of high impact nylon materials comprising block copolymers of nylon and elastomeric portions. More particularly, the present invention relates to crosslinked nylon block copolymers and methods and compositions useful for making the crosslinked nylon block copolymers. Generally, nylon block copolymers include polyamide segments and polyether, polyester,
There may be alternating blocks of other segments, such as segments of elastomeric polymer residues, such as hydrocarbon or polysiloxane residues. These nylon block copolymers are generally produced by copolymerizing lactam monomers and elastomeric polymers, and can be linear or branched depending on the structure of the elastomeric polymer used. It may be. Further details on the structure and preparation of specific types of nylon block copolymers are provided in U.S. Pat.
No. 4031164. The polyamide segments and elastomeric polymer residue segments of the nylon block copolymer defined in the above patents contribute their respective properties to the final polymer. To obtain high modulus materials, high molecular weight and/or high weight percent polyamide segments can be used. Large tensile elongation and impact properties are
This can be achieved by using high weight percent and/or high molecular weight elastomeric polymers in preparing the nylon block copolymers. It would be advantageous and an advance in the art to develop other means to alter the properties of nylon block copolymers. This invention relates to the crosslinking of nylon block copolymers through the use of polyfunctional amines. The cross-linked nylon block copolymer of the present invention can be obtained by providing a reaction mechanism in which a polyfunctional amine cross-links the nylon block copolymer. This can be accomplished, for example, by reacting an acyllactam-functional material with a polyfunctional amine to produce a cross-linked acyllactam-functional material, which is then simultaneously or subsequently reacted with a lactam monomer in the presence of a lactam polymerization catalyst. This can be accomplished by reacting to form a cross-linked nylon block copolymer. The properties of the resulting nylon block copolymer can be varied depending on the degree of crosslinking. The present invention relates to cross-linked nylon copolymers, cross-linked acyllactam-functional materials from which these nylon block copolymers can be produced, and methods for producing these cross-linked acyllactam-functional materials and nylon block copolymers. It is related to the manufacturing method. Nylon block copolymers are generally made of polyamide segments.

where Y is an alkylene group and m is an integer greater than 1, and the residues of an elastomeric polymer such as a polyether, hydrocarbon, polyester or polysiloxane or combinations thereof. Consists of blocks. A more detailed description of specific types of nylon block copolymers can be found in US Pat. No. 4,031,164, incorporated herein by reference. There are many ways to make nylon block copolymers. One common procedure involves the use of a prepolymerized elastomeric polymer (the polymer that provides the elastomeric segments in the nylon block copolymer) and a lactam monomer, where the elastomeric polymer has a lactam initiator group (and then a lactam monomer). polymerized to form polyamide segments). The lactam initiator group may be an acyllactam group, which is a known initiator of lactam polymerization. The use of elastomeric polymers prepared with acyllactam groups for the production of nylon block copolymers is disclosed in co-pending U.S. Pat. , also incorporated herein by reference). These described acyllactam functional materials can then be reacted with lactam monomers in the presence of a basic lactam polymerization catalyst to form nylon block copolymers. As mentioned above, nylon block copolymers exhibit properties conferred by elastomeric polymer residues and polyamide segments. In accordance with the present invention, it has been determined that by cross-linking a nylon block copolymer with a multifunctional amine, the overall properties of the final polymer can be changed even when the molecular weight and weight percent of the elastomeric polymer are held constant. . In one embodiment, the cross-linking is accomplished by reacting at least one acyllactam-functional material with at least one polyfunctional amine and then or simultaneously reacting the lactam monomer with the lactam monomer in the presence of a lactam polymerization catalyst. Obtained by reaction. The term "polyfunctional amine" in the present invention refers to, for example, polymers prepared with at least two primary or secondary amines, and more preferably with at least three primary or secondary amines. shall mean an organic compound such as Multifunctional amines useful in the practice of this invention may vary in molecular weight and type of organic compound. It should be noted that polyfunctional amines suitable for the present invention are of the type capable of cross-linking acyllactam functional type materials and/or nylon block copolymers. Additionally, the position of the amine functionality may be at the end of the organic compound, pendant from the organic compound, or within the organic compound, such as when the amine group is intralinear. Multifunctional amines must have at least two amine functional groups that are primary or secondary. Tertiary amines are not reactive with the acyllactam functional groups of the acyllactam functional material and therefore do not cross-link the nylon block copolymers of the present invention. However, as is known in the art, typical commercially available polyfunctional amine compositions have a distribution of polyfunctional amines that has a distribution of primary, secondary, and tertiary amines. It's okay. At least two, and more preferably three, primary or secondary amine groups that react with the acyllactam functional groups of the acyllactam functional material to form the acyllactam functional material and ultimately the nylon block copolymer. Compositions of this type are useful for the practice of this invention as long as there is a sufficient amount of polyfunctional amine to provide for cross-linking (subject to cross-linking). As mentioned above, polyfunctional amines of various types and molecular weights are useful in the practice of this invention, so long as they are capable of cross-linking the acyllactam functional material and/or nylon block copolymer. The type of polyfunctional amine used will affect the physical properties of the nylon block copolymers made therefrom. Suitable polyfunctional amines include polyether-amines, polyamines, polyester-amines and hydrocarbon-amines. Typical molecular weight ranges for these polyfunctional amines are at least about 60, more preferably from about 500 to about 100,000.
It is. The term "molecular weight" as used throughout this invention and the following examples refers to number average molecular weight as determined by procedures well known in the art. A further preferred polyfunctional amine is about 400
An alkylene group having a molecular weight in the range of ~5000
They are _C2 - _C4 polyoxyalkylene polyamines. Other preferred polyfunctional amines are about 600
Hydrocarbon-amines having a molecular weight ranging from about 100,000 to about 100,000. The most preferred polyfunctional amines are polyamines, which are generally prepared by the polymerization of alkyleneimines such as ethyleneimine, and by the polymerization of organic diamines such as alkylene diamines, which have intrachain diamines. This produces polyamines with primary and tertiary amine groups. These preferred polyamines have molecular weights ranging from about 60 to about 50,000. Examples of such polyamines are polyethylenediamines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and triethylenediamine. Polyether amines, polyester-amines and hydrocarbon-amines are prepared from polymers having functional groups that are reactive towards di- or polyfunctionalized amine monomers to yield their respective polyfunctional amines. can do. They can also be obtained by reductive amination of polyols, by cyanoethylation of polyols followed by hydrogenation, or by reaction of two equivalents of diisocyanate with each hydroxy of the polyol and with water. Other methods of preparing such polyfunctional amines are within the skill of those skilled in the art. The use of polyether-amines or other polyamines with glass temperatures below 20°C
Particularly when the polyamine has a relatively high molecular weight, it can have a substantial effect on the tensile elongation and impact properties of the nylon block copolymers made therefrom. The effect on these properties is that the nylon block copolymer is prepared on a mole-for-mole basis by the polyamine without affecting the overall properties imparted by the elastomeric polymer residues of the acyllactam-functionalized material. The amount of acyllactam-functionalized material used may be reduced. In the present invention, the term "acyllactam functional material" refers to any elastomeric polymer such as polyethers, polyesters, hydrocarbons, and polysiloxanes (i.e., nylon block copolymers) prepared with acyllactam groups. elastomeric segments). The term "acyllactam group" shall for the purposes of this invention mean carboxylic acids, sulfonic acids, phosphoacids, thiocarboxyl derivatives of carboxylic acids, or _C3 - _C14 lactam derivatives of equivalent acids. . The term "acyllactam functional group" shall mean the number of acyllactam groups that the molecule of the acyllactam functional material has. Acyllactam functional materials can be produced by any known means. Preferred acyllactam groups are derived from carboxylic acid groups. For purposes of this invention, elastomeric polymer shall mean a polymer that, when co-reacted with a lactam monomer, provides a nylon block copolymer having a tensile recovery of at least about 50%. For this test, tensile recovery is determined on a sample of dry, as-shaped polymer that is stretched to 50% of its initial length (l) and held for 10 minutes before the tension is released. Measure the length of the sample (l _r ) 10 minutes after release. The percentage of tensile recovery is
1.5l−l _r /0.5l×100. The elastomeric polymer in the nylon block copolymer composition of the present invention, although it is necessary for the nylon block copolymer to be comprised of at least 50% by weight of elastomeric polymer to determine whether it imparts the tensile recovery described above. It should be appreciated that the amount is not limited to at least 50% by weight as higher and lower amounts ranging from 10 to 90% by weight also impart improved properties to the nylon polymer. Acyllactam-functionalized materials range from about 200 to about
It is derived from an elastomeric polymer having a molecular weight in the range of 15,000, more preferably from about 1,000 to 10,000 and even more preferably from 1,000 to 6,000. Suitable acyllactam-functionalized materials are greater than 1000, preferably 2000
Larger, more preferably polyethers having a molecular weight of about 4,000 to about 8,000. Other suitable acyllactam functional materials are those derived from hydrocarbons having a molecular weight of at least 1000, preferably from about 2000 to about 5000. Other suitable acyllactam-functional materials are made from polyester-ethers or polyester-hydrocarbons, the polyester having at least 1000
are made from polyethers or hydrocarbons having a molecular weight of , and are crosslinked by di- or trifunctional acid halides. One preferred acyllactam-functionalized material _of the present invention has _the following general _{structure :} e-caprolactam and 2-pyrrolidone, more preferably 2-pyrrolidone; Z is an elastomeric polymer segment, more preferably a segment of polyether, polyester-ether, polyester-hydrocarbon, hydrocarbon or mixtures thereof; There is; A is

【formula】

【formula】

[Formula] −SO ₂ −, POR ₁ −, and mixtures thereof, more preferably

[Formula] (where b is an integer equal to 1, 2, or 3, R is selected from hydrocarbons and polyether groups,
R ₁ is alkyl, aryl, aralkyl, alkyloxy, aryloxy, aralkyloxy,
and halogen groups), and n is an integer greater than 1, preferably greater than 2, more preferably equal to 3. These suitable acyllactam functional materials generally contain R groups having a molecular weight up to 300, such as terephthaloyl halide or isophthaloyl halide (where R is phenylene) in the presence of an acid scavenger. reaction of polyethers, hydrocarbons, polyesters with polyether segments or hydrocarbon segments, or polysiloxanes (R is phenylene) with polyfunctional acid halides to give the reaction, followed by reaction with lactam monomers. Produced by reaction. However, it should be appreciated by those skilled in the art that these preferred acyllactam functional materials can be prepared by a variety of means. The "Z" segment described above has the same molecular weight limitations discussed above for elastomeric polymers useful in making acyllactam functional materials. Suitable polyether Z moieties are polyalkylene oxides such as polyethylene oxide, polypropylene oxide and poly(tetramethylene oxide). Examples of suitable polymeric hydrocarbon segments are polyethylene, polypropylene, and various polyalkenes and polyalkadienes, such as polybutadiene and copolymers of butadiene and acrylonitrile, and alkadiene copolymers. Examples of suitable polyester segments include polyether polyols such as polyoxypropylene polyols or polyoxyethylene polyols reacted with polyfunctional acid halides such as terephthaloyl chloride to form polyester ethers, or polybutadiene diols. Polyester hydrocarbons are produced by reacting polymeric hydrocarbon polyols such as terephthaloyl chloride with polyfunctional acid halides to form polyester hydrocarbons.
Examples of suitable polysiloxane segments are silicone polycarbinols and polydimethylsiloxane diols and polyols. The cross-linked nylon block copolymers of the present invention are prepared under conditions in which the acyl lactam groups of the acyl lactam functional material are reacted with the polyfunctional amine either prior to or simultaneously with the polymerization of the lactam monomer. This cross-links the acyllactam-functionalized material, which then or simultaneously polymerizes the lactam monomer, resulting in a cross-linked nylon block copolymer. According to the invention, it is suitable to use one particular type of acyllactam functional material and/or polyfunctional amine in carrying out the invention, or the acyllactam functional material described above. It should be noted that it is appropriate to use mixtures of polyfunctional amines and/or polyfunctional amines. The final nylon block copolymer is typically
It comprises at least about 10% by weight of the lactam block polymer, preferably from about 10 to about 90%, and more preferably from about 60 to about 80%. The reaction between the acyllactam-functional material and the polyfunctional amine can be carried out as a distinctly independent reaction with the subsequent added lactam monomer and basic lactam polymerization catalyst. This reaction between the acyl lactam functional material and the polyfunctional amine is carried out in an organic solvent or in a lactam monomer, such as caprolactam, at a temperature of about 100° to about 150° C. for a reasonable period of time. This can be accomplished by mixing the lactam-functional material and at least one polyfunctional amine. Lactam monomer and lactam polymerization catalyst (which is required to polymerize the lactam monomer in the production of nylon block copolymers) can then be added to the reaction. The reaction between an acyllactam-functional material and a polyfunctional amine can also be carried out in the presence of a lactam monomer and a catalyst. If this method is selected, reaction conditions can be selected to favor the reaction between the polyfunctional amine and the acyllactam functional material over the polymerization of the lactam monomer. This means that the temperature in the mixing process is approximately
Keep lower than 100℃ and then about 100℃ like in the range of 110-150℃ to increase the polymerization of lactam monomer.
This can be done by keeping the reaction temperature below the optimum temperature for lactam polymerization so as to increase the temperature above .degree. Preferably, the reaction conditions are such that after mixing the reactants, the temperature is rapidly increased to 130-130°C.
The reaction is chosen to occur simultaneously by increasing the temperature to 150°C. The amount of polyfunctional amine used for the practice of this invention should be sufficient to improve the tensile properties and/or tear strength of the nylon block copolymer. This amount is highly dependent on the molecular weight and functionality of the polyamine, with relatively small amounts being required when the molecular weight or functionality is high. at least 0.02 equivalents of polyamine per equivalent of acyllactam;
Preferably at least 0.2 equivalents, even more preferably 0.3
Advantageously, an amount of amine (primary and secondary) of ~0.6 equivalents is present. The bond between the resulting polyfunctional amine and the acyllactam group of the acyllactam-functionalized material is believed to be represented as follows: elastomer segment ~

[Formula] ~ Elastomer segment where X is a residue of a polyfunctional amine, and the bond is provided by the amine group of the polyfunctional amine, the lactam residue, and the carbonyl group of the lactam residue. As mentioned above, the polyfunctional amine from which X is derived may be located at a terminal position of the polymer molecule, pendant from the polymer molecule, or incorporated into the polymer as an interpolymer good. A typical nylon block copolymer made from a suitable acyllactam-functionalized material cross-linked by a polyfunctional amine has the general formula: where Z and A are as defined above and X is a polyfunctional amine, preferably a polyether amine, a polyester amine derived from a polyether amine or a polymeric hydrocarbon amine;
a polymeric hydrocarbon amine or polyamine, Y is alkylene or substituted alkylene having from about 3 to about 14 carbon atoms, preferably 3 or 5 carbon atoms, more preferably 5 carbon atoms; can be,
p is an integer equal to or greater than 1, preferably greater than 3, m, m ₁ , m ₂ and m ₃
are each an integer equal to or greater than 1, and n and n' are each an integer equal to or greater than 1, preferably 2 or more, more preferably 3 or more. . From the above formula of the cross-linked nylon block copolymer, it can be seen that as a result of the reaction between the acyllactam functional elastomer segment and the polyfunctional amine, the amide bond (~ NH-Y-CO-X-CO-
It should be noted that Y-NH~) is obtained. Examples 1 and 2 The following examples demonstrate two methods of cross-linking acyllactam-functionalized elastomer segments. Example 1
illustrates the process of the invention starting from the reaction of a polyol and a bisimide (or bisacyllactam) to form an acyllactam functional elastomer segment, which is then reacted with a polyfunctional amine and then a lactam monomer. Example 2 illustrates the process of the invention starting from an acyllactam-functionalized elastomer segment, cross-linking it with a polyfunctional amine, and then reacting with a lactam monomer. Two examples, 1' and 2', are used to compare the properties of cross-linked nylon block copolymers according to the present invention with such non-cross-linked nylon block copolymers. It is produced by the same procedure and from the same materials as the synthetic amine. Example 1 In a 500 ml flask, 117 g of ethylene oxide cap type polyoxypropylene triol with a molecular weight (mw) of approximately 4800 and adipyl-bis-caprolactam are added.
26.3 g, caprolactam 5 g, and Flectol H (antioxidant) 1.5 g. The mixture was heated and stirred at 125°C for 30 minutes under 1 mm vacuum, then cooled to 85°C. In a second flask, caprolactam 225
g was dried. The caprolactam was then cooled to 75° C. and 15 ml of a 3 molar solution of ethylmagnesium bromide in diethyl ether were added. The flask was evacuated to completely degas it and 3.7 g of polyoxypropylene diamine (approximately 230 mw) was admixed. The contents of both flasks were simultaneously injected into a sealed two-section Teflon-lined mold that had been preheated to 130°C. The two mold sections were separated by a 1/8" Teflon spacer. The 1/4"
The contents were injected into the mold through a 6 inch Kenix electrostatic mixer. After 5 minutes, the casting was removed from the mold.
The resulting segmented block copolymer molding contained 40% polyester. Example 2 Acyllactam functionalization by reacting ethylene oxide cap polyoxypropylene triol (mw approximately 4800), terephthaloyl chloride and excess caprolactam in the presence of triethylamine (acting as acid scavenger) in tetrahydrofuran at 40°C. The mold material was manufactured.
The molar ratio of triol to terephthaloyl chloride used to prepare this functionalized material was 2:5. A 500 ml flask was charged with 134 g of the acyllactam functional material described above and 43 g of caprolactam. The mixture was heated at a pot temperature of 140°C to distill off 25ml of caprolactam, then cooled to 85°C. A 0.23 molar bromomagnesium caprolactam solution was prepared by adding 15 ml of a 3 molar solution of ethylmagnesium bromide in diethyl ether to 200 g of dry caprolactam in a second flask. Next, polyoxypropylene diamine (m.
w. approx. 230) 2.12 ml (2.0 g) was added. The equivalent weight of the primary and secondary amines of this polyfunctional amine is 30% of the acyllactam group equivalent of the acyllactam functional type material.
It was %. Two flasks of material were injected into the mold as described above for Example 1. After 5 minutes, the casting was removed from the mold to yield a nylon block copolymer containing 40% polyester. Comparative Examples 1' and 2' Two comparative examples 1' and 2' were prepared by the same procedures and the same materials (except for the polyfunctional amine) as described above for corresponding Examples 1 and 2. The nylon block copolymer casters prepared in Examples 1 and 2 and Comparative Examples 1' and 2' were tested for various properties in accordance with essentially the following procedure: Tensile strength: ASTM 638 [units per square inch] Pound (psi) or megapascal (Mpa)
] Tear strength: ASTMD 1004 [Units are pounds per linear inch (pli) or Newtons per meter (N/M)] Tensile modulus: ASTMD 638 [Units are pounds per square inch (psi) or megapascals (Mpa) )] Tensile elongation: ASTMD638 [Unit %] The properties obtained for Examples 1 and 2 and Comparative Examples 1' and 2' are listed in the table below. As can be seen from the table, the properties of the nylon block copolymers were generally improved by cross-linking. One property that was adversely affected by cross-coupling was the bending modulus. However, for certain applications this reduction is negligible.

[Table] *Tensile recovery was determined after tensile failure.
Examples 3-9 Examples 3-9 demonstrate the use of di- and tri-functional amines to crosslink nylon block copolymers in accordance with the present invention. Acyllactam functional elastomer segment (prepared as described for Example 2 above)
A masterbatch of acyllactam functional material solution was prepared by charging 1800 g to a flask with 18 g of Frectol ODP antioxidant. The mixture was heated at 100° C. under 1 mm Hg vacuum for 1 hour with vigorous stirring to remove moisture. The mixture was then cooled to 75°C to prepare Examples 3-9.
Divide into 200g portions. A solution of 3 mol ethylmagnesium bromide in diethyl ether to 1000 g dry molten caprolactam 60
A masterbatch of 0.18 mol of caprolactam magnesium bromide (catalyst solution) in caprolactam was prepared by adding 0.18 mol of caprolactam magnesium bromide (catalyst solution) by adding 1 mmHg and then completely degassing under 1 mmHg vacuum. The amounts and types of polyfunctional amines of each of the examples as shown in the formula table were added to the catalyst solution.

[Table] Vertical Teflon lining preheated to 130℃ 2
A functional material solution and a catalyst solution containing a polyfunctional amine were pumped into the section mold. The mold sections were separated by 1/8″ Teflon spacers.
These solutions were pumped into the mold through a 1/4 inch by 6 inch Kenix static mixer with two No. 5 Zenith gear pumps at 200 rpm. The pumping ratio was 2.57 ml functional material solution to 1 ml catalyst solution. In each case, the nylon block copolymer cured to a hard resin in 30 or 60 seconds. The table below lists the properties obtained for Examples 3-9. These properties were determined as described for Examples 1 and 2 above.

【table】

[Table] *Tensile recovery was determined after tensile failure.
Examples 10-16 Examples 10-16 demonstrate the effect on the properties of nylon block copolymers crosslinked with amines of the invention using different mole percentages of diamines and triamines. Each row was prepared from a masterbatch of acyllactam functional material solution. 1067 g of functionalized material (prepared as in Example 2 above) in a 2 liter flask;
This masterbatch was produced by charging 158 g of caprolactam and 0.4 g of cupric acetate monohydrate. The mixture was dried by distilling off 25 ml of material at 140° C. under vacuum. The dried solution was kept under vacuum at 100° C. until use, at which time the vacuum was broken and replaced with nitrogen. Separate batches (200 g) of catalyst solution were prepared for each example. These individual catalyst batches were prepared by charging 193 g of caprolactam and the amounts of the amines used as shown in the table below in a 500 ml flask. The catalyst solution was dried by distilling off 25 ml of material at 140° C. under oil pump vacuum. Adjust the temperature to 125℃ and remove the catalyst concentrate.
32g was added and dissolved in each batch. The catalyst concentrate contained 1.05 mol/Kg caprolactam magnesium bromide in caprolactam. Each of the catalyst solutions produced contained 0.16 mol/Kg of caprolactam magnesium bromide. The catalyst solution was kept under vacuum at 100° C. until use, at which time the vacuum was broken and replaced with nitrogen. The table below shows the type and amount of amine used and the mole percent of amine to acyllactam groups.

【table】

[Table] The functional material solution and catalyst solution produced above
By two No. 5 Zenith gear pumps at 200rpm
The resulting nylon block copolymer mold was simultaneously pumped through a 1/4 inch Kenix electrostatic mixer in a vertical mold preheated to 130°C with dimensions of 8″ x 8″ x 1/8″. The moldings contained 40% polyoxypropylene.
Following the test procedures described above, the properties listed in Table V below were tested with the addition of a test for bend recovery, which was performed as follows; Bending Recovery - Molding was placed around a 1/2" mandrel for 30 seconds. Bend 180 degrees. Relax and read the recovery after 5 minutes. Units are percentage (%). The results of this test are shown in the table below.

[Table] Tensile elongation, tensile strength, tensile modulus and tear strength properties from about 30 to about 60 amine equivalent%
shows an improvement; after about 60% these properties decrease, but are still better than the case of Example 10. Bending recovery appeared to be worse with cross-coupling, but for some applications this has no effect. Overall, the property profile has been improved. Examples 17-20 Examples 17-20 illustrate the amount of polyether-triamine crosslinked polyether-triamine-functionalized material used to produce the nylon block copolymer according to the present invention. −
The properties of the nylon block copolymer are shown when the amount of amine is reduced. The effect on elastomeric properties provided by the polyether-amine compensated for the reduced amount of acyllactam functional material used to make the nylon block copolymer. The acyllactam functional material was prepared as described in Example 2 above. Batches of functionalized material in caprolactam solution were prepared for Examples 17-20, respectively. The respective amounts of functionalized materials and caprolactam used for each example solution are shown in the table below.

Table: Catalyst solutions were prepared for each example following the procedures described for Examples 10-16 above. Each solution yielded a concentration of 0.16 moles of caprolactam magnesium bromide per kg of caprolactam solution. Multifunctional amines were added to the catalyst solution, with type, amount and equivalents of amine functionality (primary and secondary) per equivalent of acyllactam for each example listed in the table below.

TABLE Each of the examples was tested for the properties listed in the table below according to the test procedures discussed above. The results of this test are listed below for each example and for comparison, Example 10
The characteristics are repeated.

Table: The results in the table above show that there is a significant improvement in the properties of the cross-linked nylon block copolymers. The above results also show that significant improvements can be obtained with multifunctional amines when the amine functionality (primary and secondary) is at least 3. Although preferred embodiments have been described above, various substitutions and modifications can be made thereto without departing from the scope of the invention. Accordingly, it is to be understood that the invention has been described by way of illustration (and not limitation).

Claims (1)

[Claims] Primary formula () to ()': -A-O-Z--(O-A-) _o () -X-() _p () -CO-Y-NH- () , [wherein each A is independently -CO-R--(CO
−) _b , −CO−CO−, −CO−, −SO ₂ −, or −
POR ₁ − (b is 1, 2 or 3, R
is a hydrocarbon group or polyether group with a molecular weight of 300 or less, and R ₁ is alkyl, aryl, aralkyl, alkyloxy, aryloxy, aralkyloxy or halogen. ), Z each independently represents polyether, hydrocarbon,
represents an elastomer segment made of polyester, polysiloxane, or a mixture thereof containing polyether or hydrocarbon and the above A; each Y independently represents an alkylene having 3 to 14 carbon atoms; each n independently represents 1, 2 or 3; , p each independently represents an integer of 1 or more, O represents an oxygen atom, N represents a nitrogen atom, C represents a carbon atom, and H represents a hydrogen atom. ] The three types of segments represented by formula () constitute an amide bond, and the molecular weight of the segment of formula () is 200 to 15,000.
and the molecular weight of the segment of formula () is 60 to 100000
and the segment of expression () is connected to the segment of expression () through the segment of expression ()′, or
or the following formula (): A cross-linked nylon block terminal-terminated by bonding to a lactam ring of the formula (), wherein the equivalent ratio of the segment of the formula () to the sum of the segment of the formula ()′ and the lactam ring of the formula () is at least 0.02. Copolymer Elastomeric copolymer for the production of high impact nylon materials. 2. The polymer of claim 1, wherein the segment of formula () has a molecular weight of at least 1000 and Z is a polyether or a hydrocarbon. 3. The polymer according to claim 1, wherein the segment of formula () has a molecular weight of 60 to 50,000. 4. The polymer according to claim 1, wherein the segment of formula () has a molecular weight of 400 to 5000, and X is a polyamine containing polyether. 5. The polymer according to claim 1, wherein the ratio of amounts is at least 0.2. 6. The polymer according to claim 1, wherein the ratio of amounts is 0.3 to 0.6. 7. The polymer according to claim 1, wherein Y is -( _CH2- ) ₃ or -( _CH2- ) ₅ . 8. The polymer according to claim 1, wherein A is -CO-R-(CO-) _b . 9 The following formula () to (): -A-O-Z-(O-A-) _o () -X-() _p () -(CO-Y-NH-) _n () [In the formula, A are each independently −CO−R−(CO
−) _b , −CO−CO−, −CO−, −SO ₂ −, or −
POR ₁ − (b is 1, 2 or 3, R
is a hydrocarbon group or polyether group with a molecular weight of 300 or less, and R ₁ is alkyl, aryl, aralkyl, alkyloxy, aryloxy, aralkyloxy or halogen. ), Z each independently represents polyether, hydrocarbon,
Represents an elastomer segment made of polyester, polysiloxane, or a mixture thereof containing polyether or hydrocarbon and the above A, and each X independently consists of polyamine, or polyether, polyester, hydrocarbon, or polyamine containing them. represents the residue of a polyfunctional amine having at least two primary or secondary amine functions, each Y independently represents alkylene having 3 to 14 carbon atoms, each n independently 1, 2 or 3 , p each independently represents an integer of 1 or more, m each independently represents an integer of 1 or more, O represents an oxygen atom, N represents a nitrogen atom, C represents a carbon atom, and H represents a hydrogen atom. ] The three types of segments represented by formula () constitute an amide bond, and the molecular weight of the segment of formula () is 200 to 15,000.
and the molecular weight of the segment of formula () is 60 to 100000
and segments of expression() are combined with segments of expression() via segments of expression(), or segments of expression() via segments of expression(): A cross-linked nylon block copolymer for use in high-impact nylon materials, characterized in that the copolymer is terminal-terminated by bonding with a lactam ring. 10. The copolymer of claim 9, wherein the segment of formula () has a molecular weight of at least 1000 and Z is a polyether or a hydrocarbon. 11. The copolymer according to claim 9, wherein the segment of formula () has a molecular weight of 60 to 50,000. 12. The copolymer according to claim 9, wherein the segment of formula () has a molecular weight of 400 to 5000, and X is a polyamine containing polyether. 13. A copolymer according to claim 9, in which the relevant ratio is at least 0.2. 14. The copolymer according to claim 9, wherein the ratio of amounts is 0.3 to 0.6. 15. The copolymer according to claim 9, wherein Y is -( _CH2- ) ₃ or -( _CH2- ) ₅ . 16. The copolymer according to claim 9, wherein A is -CO-R-(CO-) _b . 17 The following formula () ~ (): -A-O-Z-(O-A-) _o () -X--() _p () -(CO-Y-NH-) _n () [In the formula, A is each independently -CO-R--(CO
-) represents _b ,, -CO-, -CO-, -CO-, _-SO2- , or _-POR1- (b is 1, 2 or 3,
R is a hydrocarbon group or polyether group having a molecular weight of 300 or less, and R ₁ is alkyl, aryl, aralkyl, alkyloxy, aryloxy, aralkyloxy or halogen. ), Z each independently represents polyether, hydrocarbon,
represents an elastomer segment made of polyester, polysiloxane, or a mixture thereof containing polyether or hydrocarbon and the above A; each Y independently represents an alkylene having 3 to 14 carbon atoms; each n independently represents 1, 2 or 3; , p each independently represents an integer of 1 or more, m each independently represents an integer of 1 or more, O represents an oxygen atom, N represents a nitrogen atom, C represents a carbon atom, and H represents a hydrogen atom. ] The three types of segments represented by formula () constitute an amide bond, and the molecular weight of the segment of formula () is 200 to 15,000.
and the molecular weight of the segment of formula () is 60 to 100000
and segments of expression() are combined with segments of expression() via segments of expression(), or segments of expression() via segments of expression(): In the method for producing a cross-linked nylon block copolymer for high-impact nylon material, the cross-linked nylon block copolymer is terminal-terminated by bonding with a lactam ring of the following formula (): Z-[O-A-(Q) _b ] _o+1 ( ) [wherein Q represents a C ₃ to _{C 14} lactam ring of formula (). ] Acyllactam functional type material: The following formula (): A polyfunctional amine of the following formula (): X-(H) _p+1 (); The following formula (): a _C3 - _C14 lactam of the above formula (); and a lactam polymerization catalyst;
the equivalent ratio of the _C3 to _C14 lactam of the above formula () to the acyl lactam functional material of the above formula () is at least 0.02;
Acyllactam functional type material and the above formula ()
The method is characterized in that the weight ratio of the polyfunctional amines is in the range of 9:1 to 1:9. 18. The method of claim 17, wherein the segment of formula () has a molecular weight of at least 1000 and Z is a polyether or a hydrocarbon. 19. The method according to claim 17, wherein the segment of formula () has a molecular weight of 60 to 50,000. 20. The method of claim 17, wherein the segment of formula () has a molecular weight of 400 to 5000 and X is a polyamine including polyether. 21. The method of claim 17, wherein the ratio of amounts is at least 0.2. 22. The method according to claim 17, wherein the ratio of amounts is 0.3 to 0.6. 18. The method according to claim 17, wherein 23Y is -( _CH2- ) ₃ or -( _CH2- ) ₅ . 24. The method according to claim 17, wherein A is -CO-R-(CO-) _b . 25. The method of claim 17, wherein the mixing step is carried out at a temperature below 110°C and the polymerization step is carried out at 110-150°C.