JPS60127325A - Manufacture of nylon block copolymer - Google Patents

Abstract

PURPOSE:To obtain titled copolymer with excellent properties, colorable to any desired color since it is inherently colorless, by performing polymerization, using a basic catalyst, of lactam in the presence of terminal acylimidazole group-carrying matter. CONSTITUTION:The objective copolymer can be obtained by polymerization of (A) lactam, in the presence of (B) a matter having terminal acylimidazole group of formula (R1 is divalent hydrocarbon; R2 and R3 are each H, alkyl or aryl; R4 is divalent aliphatic hydrocarbon; m>=2; l>=1) using (C) a basic lactam polymerization catalyst (e.g. alkali metal). The component (B) can be prepared, for example, by the reaction between (1) polyether diol such as polypropylene glycol and (2) divalent carboxylic acid imidazolide such as isophthaloyl bisimidazolide. EFFECT:Providing articles with extremely bright color.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a Chiron block copolymer using a material having an acylimidazole end. More specifically, the present invention involves polymerizing a lactam with a basic lactam polymerization catalyst in the presence of a material containing a polyether polymer moiety having two or more acylimidazole ends to form a nylon block copolymer. The present invention relates to a method for producing a polymer.

Regarding the production method using basic lactam polymerization catalyst,
Patent application publication 1984-40120.

U.S. Patent 8,862,262.4,031.164゜4
．． 034,015 and 4,228,112, etc., and it has been shown that this block copolymer can be used for applications such as textile fibers, foam, furniture, and automobile parts by taking advantage of its excellent properties. There is. One of the major drawbacks of the nine-a block copolymer obtained by the method of the patent is that the copolymer is yellow colored.

Since the copolymer itself is colored yellow, not only is it impossible to obtain a colorless product, but even when it is desired to color the product in a desired color, only a dull color is obtained. This is unfavorable from the aesthetic point of view of the product.

In order to improve these drawbacks, the present inventors have conducted intensive research on a method for obtaining a nylon block copolymer that is colorless and has excellent properties, and as a result, has arrived at the present invention.

The present invention provides lactams with the formula (wherein VLl is a divalent hydrocarbon group, R2 and R,
is a hydrogen atom or a group selected from alkyl and aryl groups, 艮 is a divalent aliphatic hydrocarbon group, 1ml is an integer of 2 or more, and e is an integer of 1 or more). The present invention relates to a method for producing a nylon block copolymer, which is characterized by polymerization using a basic lactam polymerization catalyst in the presence of a substance containing a nylon block copolymer.

The lactams used in the present invention are lactams that undergo ring-opening polymerization, such as caprolactam, pyrrolidinone, piperidone, valerolactam, capryllactam,
Examples include lauryl lactam. Also included are lactams having substituents that do not adversely affect the polymerization of the lactam.

The acylimidazole-terminated substances used in the present invention are polyether diols represented by the formula % (wherein R1 is a divalent hydrocarbon group and m is an integer of 2 or more) and the formula ( In the formula, X is a halogen atom, and 4 is a divalent hydrocarbon group. It can be produced by reacting -I and these reactions are represented by the following reactions I and U.

Reaction (2) Reaction (2) The acylimidazole-terminated substance used in the present invention can also be produced by the method shown in Reaction (2) in which polyether diols and divalent carboxylic acid imidazolide 7 are reacted.

This method is based on the Industrial Chemistry Journal, Vol. 72, No. 7, p. 1608, p. 196.
It is also described in 1999 (published by the Chemical Society of Japan).

Reaction ■ 11-HO+ILs 0+ H+(g+t) ・JuZ
g-1-1-N back s Here, 4 is an integer of 1 or more, up to about 20.

In addition, the imidazolide of divalent carboxylic acid can be synthesized by a known method. It can be synthesized by mixing a divalent carboxylic acid halide and an imidazole in a solvent in the presence or absence of a dehydrogenating agent.

In the polyether diol represented by HO+λ1-0+H used in the reactions I and (1) above, m is an integer of 2 or more.艮1 is a divalent aliphatic hydrocarbon group, for example.

The number average molecular weight of the polyether diol is generally 500 or more, particularly preferably t,ooo to 6.000. The number average molecular weight of the polyether diol is 5
If it is less than 00, the impact strength of the final nylon block copolymer will not increase, and if it exceeds 6,000, the terminal OH group concentration of the polyether diol will be low, resulting in the formation of a nylon block copolymer. This is not desirable because it becomes

Examples of the λ4 group of the halide of the divalent carboxylic acid used in the reaction ① and the λ4 group of the divalent carboxylic acid imidazolide used in the reaction ① include -cHQ-, -C2
H4-(succinate), -Ci1%-(gny9-
)), -C,H8-(7dipate), -CsHto-(
pimelate), -CaHll-(7,heL/-))
, -c-I'14-(y cel/-卜), -cN min
etc.

The halide of divalent carboxylic acid in reaction I and the imidazolide of divalent carboxylic acid in reaction (2) have an acyl halide group in the halide of divalent carboxylic acid, or The T-syl imidazole group in the dihydric carboxylic acid imidazolide is 1.
It is used in an amount of 01 to 2.0 equivalents, preferably 1.05 to 1.8 equivalents, and if it is less than i, oi equivalents, the molecular weight of the acyl halide-terminated polyether or acylimidazole-terminated polyether will increase too much. Inconveniences occur such as not all the ends of the polyether are acyl halide ends or acylimidazole ends, and if the value exceeds 2.0, unreacted halides of divalent carboxylic acids or imidazolides of divalent carboxylic acids are attached in large numbers. R is preferable because it remains.

The imidazole units in the dihydric carboxylic acid imidazolide in reaction (1) and (2) are preferably hydrogen, methyl, ethyl, propyl, inpropyl, butyl, imbutyl, tert-butyl, pentyl, phenyl, tolyl. Those selected from the groups such as imidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-methyl-4-methylimidazole, 2-methyl-4-ethylimidazole are particularly preferred. 2-Methyl-4-propylimidazole, 2-ethyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2-ethyl-
4-propylimidazole, 2-phenyl-4-methylimidazole, etc. are used.

These imidazoles used in reaction U are used in an amount of 1 to 4 equivalents per 1 equivalent of the acyl halide group of the acyl halide-terminated polyether, and if the amount is less than 1 equivalent, the terminal acyl halide group of the polyether remains, and if the amount is 4 equivalents or more, the acyl halide group of the polyether remains. This is economically unfavorable since a large amount of unreacted imidazole remains.

The reaction of polyether diol and halide of dihydric carboxylic acid in Reaction I can be carried out by a known method.

That is, in general, a polyether diol and a dicarboxylic acid halide are mixed together, preferably in the presence or absence of a solvent, and in the presence or absence of a dehydrohalogenating agent such as a tertiary amine. A polyether having an acyl halide end can be synthesized by carrying out a mixed reaction at a temperature of 40°C to 150°C.

Furthermore, the reaction between a polyether having an acyl halide end and an imidazole shown in Reaction I is generally carried out by reacting the polyether having an acyl halide end with an imidazole in the presence or absence of a solvent, such as a tertiary amine, etc. The mixture reaction is carried out in the presence or absence of a dehydrohalogenating agent, preferably at a temperature of 0°C to 150°C, and the hydrogen halide salt of the tertiary amine or imidazole is separated from door to door. It will be done.

The reaction between the dihydric carboxylic acid imidazolide and the polyether diol shown in reaction (2) is generally carried out by reacting the divalent carboxylic acid imidazolide and the polyether diol in the presence or absence of a solvent, preferably at a temperature in the range of -40°C to 150°C. This is done by mixing and reacting.

The method for producing the nylon block copolymer of the present invention generally involves mixing at a lower temperature than the acylimidazole-terminated polynylene obtained in reaction I or (2) above, and then heating to a temperature at which the lactam can polymerize to open the ring. Obtained by polymerization. The mixing ratio of the acylimidazole-terminated polyether and the lactam is generally such that the acylimidazole-terminated polyether is used in an amount of 5% to 70% by weight, preferably 6% to 60% by weight based on the total weight of the two. If the amount is less than 5% by weight, the impact strength of the nylon block copolymer will not be exhibited, and if it exceeds 70% by weight, the rubber elasticity will be lost, which is not preferable.

A nylon block copolymer with a small proportion of the acylimidazole-terminated polyether moiety becomes a hard resin with excellent impact resistance and heat resistance, and a large proportion exhibits rubber-like properties.

As basic lactam polymerization catalysts, rough''/, (
7) A group of compounds recognized as 1"a5 basic catalysts for anhydrous polymerization. In general, all alkali metals or alkaline earth metals are in the form of metals or in the form of hydrides, halohydrides, Effective catalysts include alkyl halides, oxides, hydroxides, carbonates, etc. Also useful are organometallic compounds of the aforementioned metals, such as metal alkyls, metal phenyls, metal amides, etc. Specific examples include sodium hydride, Potassium hydroxide, lithium oxide, ethylmagnesium bromide, calcium fluorohydride, strontium carbonate, barium hydroxide, methyl sodium,
Examples include butyllithium, sodium amide and diethylmagnesium. All of these compounds react with lactams to form metal lactams, which are active catalysts in lactam polymerization. Thus, metal lactam catalysts can be formed by reacting the metal or metal compound with the lactam in the polymerization system or by reacting the metal or metal compound with the lactam beforehand. Examples of metal lactam catalysts include sodium caprolactam, furomomagnesium caprolactam, magnesium caprolactam, bromomagnesium pyrrolidinone, chlorocalcium caprolactam, and the like.

The basic lactam polymerization catalyst is generally 0.1% to 10% by weight, preferably 0.5% to 10% by weight relative to the lactam.
If it is used in an amount of 5% by weight, less than 0.1% by weight will cause problems such as the polymerization rate becoming too slow and a large amount of unreacted lactam will remain, while if it exceeds 10% by weight, This is not preferable because it reduces physical properties.

In addition to the halide of dicarboxylic acid, which is the raw material for reaction (1), and the imidazolide of dicarboxylic acid, which is the raw material for reaction (2), there is a polycarboxylic acid RI which is larger than divalent carboxylic acid! (C0
Halides and imidazolides of OH) n (wherein K6 is a hydrocarbon group with a valence of more than 2 and n is an integer of more than 2) can also be used as part or all of the respective raw materials. vL of such polyhydric carboxylic acid
For example, it is most preferable to use a dicarboxylic acid as the S group.

The block copolymer obtained by the method of the present invention has a formula polymerization moiety (2 represents xl and x2, which is an integer greater than l), R1 and R4 are divalent hydrocarbon groups, and m is a divalent hydrocarbon group of 2 or more. an integer, and e is an integer of 1 or more].

The nylon block copolymer obtained by the present invention has excellent properties in addition to the aesthetic feature of being colorless, so it can be used for many end uses, such as fibers, foams, various parts, etc. . The copolymer can be put into the form of a conventional molding resin (such as pellets) and then molded into various shapes by injection molding, extrusion molding or other molding methods, or the raw ingredients can be directly molded into molds. By polymerizing in a medium, it is also possible to obtain large-sized objects such as furniture and automobile parts. The copolymers can also be used in various applications by modification with pigments, dyes, fibers, flame retardants, fillers, plasticizers, stabilizers and other additives. As mentioned above, since the copolymer itself is colorless, when it is colored with a pigment or dye, it is possible to obtain an extremely colorful i-product.

EXAMPLES The present invention will be explained in more detail by way of Examples below, but the present invention is not limited by the Examples.

Example 1 [Synthesis of imidazolide-terminated polypropylene glycol] A 2, Q 0 wzlml round bottom flask equipped with a stirring device was replaced with hydrogen, and under nitrogen, too much polypropylene glycol (number average molecule 118,000) and 15 tons of inphthaloyl bisimidazolide were added. In addition, the mixture was reacted at 100° C. for 6 hours to synthesize imidazolide-terminated polypropylene glycol.

[Synthesis of block copolymer]

Dehydrated caprolactam 8B, 6f and caprolactam magnesium bromide 1.5f were charged into a 100 ml flask purged with nitrogen and dissolved with stirring at 70°C. 15 tons of the imidazolide-terminated polypropylene glycol was added to the flask, mixed at 70°C, and then poured into a mold heated to 140°C.

A white plate-shaped resin was obtained in 4 minutes, and its physical properties were hardness (Shore D) of 48 and impact strength (notched Izod) of 22.
It was K9M7cm.

Example 2 Dehydrated caprolactam 429 and phenylmagnesium bromide 2f were charged into a 100-ml flask purged with nitrogen and dissolved with stirring at 70°C. Example 1 into the flask
6t of the imidazolide-terminated polypropylene glycol synthesized in step 1 was added, mixed at 70°C, heated to 140°C, and poured into a heated mold.

A white plate-shaped resin is obtained in 6 minutes, and its physical properties are hardness (Shore D) 76 and impact strength (notched Izod) 6Kp.
It was α/Kuni.

Comparative Example 1 Dehydrated caprolactam 469 and phenylmagnesium bromide 2 in a 100 ml flask purged with nitrogen
f was charged and dissolved with stirring at 70°C. The imidazolide-terminated polypropylene glycol 2f synthesized in Example 1 was added to the flask, mixed at 70°C, and heated to 140°C.
It was injected into the mold.

No polymerization occurred even after 1 hour.

Example 3 [Synthesis of imidazolide-terminated polytetramethylene glycol] After purging a 200 ml round bottom flask equipped with a stirring device with nitrogen, polytetramethylene glycol (
LOOP (number average molecular weight 2000) and terephthaloylimidazolide 17,8F were added and reacted at 100°C for 6 hours to synthesize imidazolide-terminated polytetramethylene glycol.

[Synthesis of block copolymer]

Dehydrated caprolactam 289 and caprolactam magnesium bromide 2f were placed in a 100@l flask purged with nitrogen and dissolved with stirring at 70°C. Add the above imidazolide-terminated polytetramethylene glycol 20 into the flask. After mixing at 70°C, the mixture was poured into a mold heated to 140°C. A white plate-like resin was obtained in 4 minutes, and its physical properties were measured for hardness (Shore D) of 28 and impact strength (notched Izod), but it did not sag.

Comparative Example 2 7 tons of dehydrated caprolactam and 2 tons of phenylmagnesium bromide were placed in a 100 ml flask purged with nitrogen and dissolved with stirring at 70°C. The imidazolide-terminated polytetramethylene glycol 411 synthesized in Example 8 was added to the flask, mixed at 70°C, and then poured into a mold heated to 140°C.

Even after 1 hour had passed, it did not become a solid resin.

Claims (1)

[Claims] Lactam is represented by the formula (wherein K1 is a divalent hydrocarbon group, yL2 and Rs are groups selected from hydrogen atoms, alkyl groups and aryl groups, and K4 is a divalent aliphatic hydrocarbon group) , m is an integer greater than or equal to 2,
and e is an integer of 1 or more) A method for producing a nylon block copolymer, characterized in that the combination is carried out using a basic lactam polymerization catalyst in the presence of a substance having an acylimidazole terminal represented by: