JPS60155230A - Production of nylon block copolymer - Google Patents

Abstract

PURPOSE:To obtain a colorless nylon block copolymer of excellent impact resistance, by polymerizing an oxycarbonyllactam group-terminated prepolymer with a lactam in the presence of a basic lactam polymerization catalyst. CONSTITUTION:An oxycarbonyllactam group-terminated prepolymer obtained by reacting a polyoxycarbonyllactam of the formula with a polyether-polyol is polymerized with a lactam in the presence of a basic lactam polymerization catalyst. In the formula, R1 is a 2-12C aliphatic group, R2 is a 2-14C aliphatic group, and n is 1-5. As the polyether-polyols, those having a number-average MW of, generally, 500 or above, particularly preferably, 1,000-6,000 are used. When the number-average MW of the polyether-polyol is below 500, the impact resistance of the finally obtained nylon block copolymer is not sufficient, while when this MW is above 6,000, the nylon block copolymer can hardly be produced, which is not desirable.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a nylon block copolymer having excellent impact resistance. More specifically, the present invention relates to a method for producing a polyether polymer portion and a nylon block copolymer containing a polyether polymer portion using a basic lactam polymerization catalyst.

A method for producing a nylon block copolymer containing a polyether polymer portion and a polylactam polymer portion using a basic lactam polymerization catalyst is disclosed in Patent Application Publication No. 1983-4.
0120, U.S. Patent 8,862,262.4,081,
164.4,084,015 and 4,228.112
It has been shown that this block copolymer can be used for textile fibers, foam, furniture, automobile parts, etc. by taking advantage of its excellent properties.

One of the major drawbacks of the nylon block copolymer obtained by the method of the patent is that the copolymer is yellow colored. Even if the copolymer itself is yellow, only a dull color can be obtained.

This is unfavorable from the aesthetic point of view of the product.

Further, German Published Patent Application No. 1.909.6'l'l describes that anionic polymerization of lactam can be carried out using a polyoxycarbonyl lactam compound as shown in the following formula as an activator.

However, the purpose of this patent is to produce polyamide by homopolymerization of lactam, and is not intended to produce a block copolymer of polyoxyalkylene and polyamide as in the method of the present invention.

The present inventors have completed the present invention as a result of intensive research into a method for obtaining a nylon block copolymer that is colorless and has excellent properties in order to improve the drawbacks of the prior art.

That is, the present invention involves polymerizing a lactam and a prepolymer having an oxycarbonyl group at the terminal, which is obtained by reacting a polyoxycarbonyl lactam compound represented by formula (I) with a polyether polyol, in the presence of a basic lactam polymerization catalyst. This is a method for producing a nylon block copolymer characterized by the following.

The polyoxycarbonyl lactam compound used in the present invention is produced by a method using N-chlorocarbonyl lactam and di- or polyol as raw materials, as shown in West German Published Patent Application No. 1,909,577.
As shown in No. 98, it is synthesized by a method using a lactam and a di- or polychloroformate as raw materials, or by a method by transesterification of a monooxycarbonyl lactam compound and a di- or polyol compound.

Examples of lactams used to produce polyoxycarbonyl lactam compounds include piperidinone, pyrrolidinone, ε-caprolactam, capryllactam, and lauryllactam. Also included are lactams having substituents that do not adversely affect the polymerization of the lactam.

The polyols used to produce the polyoxycarbonyl lactam compound include diol, 2,2
-dimethino 3, aM pandiol, hexahydroxylinol, trimethylolpropane, diethylene glycol, triethylene glycol, pentaerythritol, 1,8-cyclohexanediol, l,4-cyclohexanediol, pinacol, benzopyrene glycol, 2,8-dihydroxybutane , sorbitol, sucrose, glucose, etc.

The polyether polyol used in the present invention has the formula % (in the formula, j is an integer of 1 to 5, and 1m is an integer of 2 or more.) R3 is hydrogen or a polyol hydrocarbon residue. For example, CH3 -CHz -0H2-, -0H-CH2-, -CJz-
CH2-CH2-.

etc. R4 is a divalent aliphatic hydrocarbon group, for example -0H2-OH2-.

(Jla -OH-OHz -, -0H2-CH2-OH2-, -
CH2-cHs-OHy-JDHy-.

OHz -0-CH2- and the like.

Generally, the number average molecular weight of polyether polyol is 500.
Above, those having l,000 to 6,000 are particularly preferably used. If the number average molecular weight of the polyether polyol is less than 500, the impact strength of the finally obtained nylon block copolymer will be insufficient, with a number average molecular weight of 6.000.
Exceeding this is not preferable because the terminal OH group concentration of the polyether polyol becomes low, making it difficult to form a nylon block copolymer.

These polyether polyols can be produced by known methods, such as a method in which a cyclic ether is subjected to ring-opening polymerization using a cationic polymerization catalyst, or a method in which a cyclic ether is subjected to ring-opening polymerization using an anionic polymerization catalyst. For example, there is a method shown in KaimW Go (I), written by Takeo Saegusa and published by Aji Kagaku Doujin. Moreover, many types of polyether polyols are commercially available, and these may be used.

To prepare the prepolymer having an oxycarbonyl lactam group at the end of the present invention, the OH
The polyoxyphtam group of the polyoxycarbonyl lactam compound is 1. If the amount of O is less than 1 equivalent, the molecular weight of the prepolymer will be too high or the polyether will not be strong enough.

The reaction temperature in the reaction to obtain the prepolymer is 0°C or higher2
00°C or less, preferably 10°C or more and 160°C or less. If the reaction temperature is less than 0°C, the reaction rate will be significantly slowed, and if it exceeds 200°C, decomposition reactions such as ring opening of the oxycarbonyl lactam groups at the terminals of the prepolymer will occur, which is not preferred.

In the reaction to obtain a prepolymer having an oxycarbonyl lactam group at the end from a polyoxycarbonyl lactam compound and a polyether polyol, the polyoxycarbonyl lactam compound and polytertyl polyol are reacted with a suitable catalyst in the presence or absence of a suitable solvent. react in the presence or absence of

When a solvent is used, the polyether polyol and the polyoxycarbonyl lactam compound are difficult to mix, and the use of a solvent allows the two to mix well, making it easier to react. Further, especially when a catalyst is used, if a solvent is used, the polyoxycarbonyl lactam compound, polyether polyol, and the catalyst are well mixed, and as a result, the reaction promoting effect of the catalyst is enhanced.

Examples of solvents used in the reaction to obtain the prepolymer include methylene chloride, chloroform, carbon tetrachloride, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, cyclohexanone, dimethyl formamide, dimethyl sulfoxide, dimethyl cellosolve, diglyme,
Examples include benzene, toluene, xylene, carbon disulfide, and lactam compounds used at temperatures above the melting point, such as pyrrolidinone, piperidinone, and C-caprolactam. When a lactam compound is used as a solvent, the reaction temperature is lo.

Among organometallic compounds, lactam metal compounds are preferably used as the catalyst. For example, caprolactam magnesium chloride, caprolactam magnesium bromide, caprolactam magnesium iodide,
Compounds such as pyrrolidinone magnesium bromide, piperitone magto linenium bromide, caprolactam potassium, caprolactam lithium, and caprolactam potassium. °The polyoxycarbonyl lactam compound and the polyether polyol are reacted, and the polyoxycarbonyl lactam that is used at the terminal is the ease of handling of the prepolymer, and the bisoxycarbonyl lactam compound is , in combination with polyether diol. In that case, the prepolymer is considered to have the structure shown by the formula.

A prepolymer having an oxycarbonyl lactam group at the terminal synthesized as described above and a lactam are copolymerized using a basic lactam polymerization catalyst. Examples of the lactam include piperidinone, pyrrolidinone, e-caprolactam, capryllactam, lauryllactam, and dodecyl. Examples include lactams. Also included are lactams having substituents that do not adversely affect the polymerization of the lactam.

A specific method for obtaining a nylon block copolymer by anionically copolymerizing a lactam and a prepolymer having an oxycarbonyl lactam group at the terminal synthesized as described above is as follows.
First, the prepolymer, lactam, and basic lactam polymerization catalyst are mixed at a temperature higher than the melting point of the lactam but as low as possible.

If the temperature is below the melting point, sufficient mixing will not be possible, and if the temperature is high, a polymerization reaction will occur during mixing, so this is not preferable (1).

Polymerization is carried out by raising the temperature or by pouring into a heated container or mold.

The polymerization temperature varies depending on the type of lactam, but it is 100~
The temperature is about 200°C. For example, when d-caprolactam is used as the lactam, the mixing temperature of the prepolymer, C-caprolactam, and basic lactam polymerization catalyst is 68 to 1
00°C is preferable, and the polymerization temperature is preferably 100 to 200°C.

If the temperature is less than 100°C, polymerization will occur, and if it exceeds 200°C, the coloring will become significant, which is not preferable.

The mixing ratio of the prepolymer and lactam is 5% to 70% by weight, preferably 1% by weight of the prepolymer based on the total of both.
It is used in the range of 0% to 60% by weight, and if it is less than 5% by weight, the impact strength of the nylon block copolymer will be difficult to develop. , QM amount % is not preferable because the rubber elasticity is lost.

A resin with a small proportion of the prepolymer part contained in the nylon block copolymer becomes a hard resin with excellent impact resistance and heat resistance, and a resin with a large proportion exhibits properties as rubber.

The basic lactam polymerization catalyst includes a group of compounds that are generally recognized as suitable basic catalysts for the anhydrous polymerization of lactams. In general, all alkali metals or alkaline earth metals, either in metal form or in the form of hydrides, halohydrides, alkyl halides, oxides, hydroxides, carbonates, etc., are effective catalysts. Also useful are organometallic compounds of the aforementioned metals, such as metal alkyls, metal phenyls, metal amides, and the like. Specific examples include sodium hydride, potassium hydroxide, lithium oxide, ethylmagnesium bromide, calcium fluorohydride, strontium carbonate, barium hydroxide, methylsodium, butyllithium, sodium amide and diethylmagnesium. All of these compounds react with lactams to form metal lactams, which are active catalysts in lactam polymerization. Accordingly, 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 caprolactam sodium, caprolactam magnesium bromide, caprolactam magnesium, pyrrolidinone magnesium bromide, caprolactam calcium chloride, 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 is more than 10% by weight, the physical properties of the nylon block copolymer produced. This is not preferable because it lowers the As one form of production of the nylon block copolymer of the present invention, it can also be carried out as a series of reactions in the coexistence of eight starting materials: a polyoxycarbonyl lactam compound, a polyether polyol, and a lactam. In the presence of a basic lactam polymerization catalyst, the 8 components are first maintained at a temperature of 100° C. or lower, at which lactam homopolymerization does not occur, and the polyoxycarbonyl lactam compound and polyether polyol are reacted to form a prepolymer.

Subsequently, the prepolymer and the lactam are copolymerized by maintaining the temperature at 100° C. or higher at which polymerization of the lactam occurs.

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: Since the copolymer itself is colorless, it can be colored with pigments or dyes to produce extremely brightly colored products.

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

Example 1 [Synthesis of prepolymer] After purging a 200 mm round bottom flask equipped with a stirring device with nitrogen, polypropylene glycol (number average molecular weight 2000) 45 kg, tetramethylene glycol (1,
4)-Bis(N-oxycarbonylcaprolactam)t
2.69 and caprolactam magnesium bromide 0.589 were charged and reacted at 120° C. for 1 hour with stirring to obtain a prepolymer.

[Synthesis of nylon block copolymer]

In a 100mm round bottom flask purged with nitrogen, 29 g of dehydrated caprolactam and 1.47 g of caprolactam magnesium bromide were charged and dissolved with stirring. Add the prepoly v-19,6P into the flask and mix at 70°C,
The mixture was poured into a mold heated to 140°C. A white plate-shaped resin was obtained in a polymerization time of 8 minutes, and its physical properties were hardness (Shore D
)55. Impact resistance strength (Izot with notch) 20Qα/
It was cII.

Example 2 [Synthesis of prepolymer] Polypropylene glycol (number average molecular weight 2000) 4
Using 12.6 F, tetramethylene-(1,4)-bis(N-oxycarbonyl caprolactam), 80 g of caprolactam, and 0.589 g of caprolactam magnesium bromide, the reaction temperature and reaction time were 70'C and 145 minutes, respectively. A prepolymer 1 was obtained in accordance with Example 1 except for the following steps.

[Synthesis of nylon block copolymer]

Dehydrated caprolactam 195' and caprolactam magnesium bromide 1.47F were charged into a 100° round bottom flask purged with nitrogen, and dissolved with stirring. The prepolymer at 29.6 F was added to the flask, mixed at 70°C, heated to 140°C, and poured into a mold. A white plate-like resin was obtained in 10 minutes of polymerization, and its physical properties were hardness (
Shore D) 57. Impact resistance (Izot with notch)
28 Immediate Cal/C11.

Comparative Example 1T Homopolymerization of Nylon] 25 g of dehydrated caprolactam and 0.89 g of caprolactam magnesium bromide were placed in a nitrogen-substituted 100 mm round bottom flask and dissolved with stirring. 0.5 of tetramethylene-(1,4)-bis(N-oxycarbonylcaprolactam) in the flask! Caprolactam 25F in which M' was dissolved was added, mixed at 70°C, and then poured into a mold heated to 140°C. A white plate-shaped resin was obtained in a polymerization time of 10 minutes, and its physical properties were hardness (Shore D) of 8B,
Impact resistance strength (Izot with notch) 8r4・cll/C
It was I+.

Example 8 [Synthesis of prepolymer] Polypropylene glycol (number average molecular weight 2000) 4
A prepolymer was obtained according to Example 1, except that 5F, cyclohexane-(1,4)-bis(N-oxycarbonylcaprolactam) 18.55', and caprolactam magnesium bromide 0.58 y were used.

[Synthesis of nylon block copolymer]

Dehydrated caprolactam 28.8P and caprolactam magnesium bromide 1.47F were charged into a 100-mm round bottom flask purged with nitrogen and dissolved with stirring. 19. of the prepolymer into the flask. 'M- was added, mixed at 70°C, and then poured into a mold heated to 140°C. A white plate-shaped resin was obtained in a polymerization time of 8 minutes, and its physical properties were a hardness (Shore 1) of 60. Impact resistance strength (Izot with notch) 2
5 immediately and alI10+.

Claims (1)

[Scope of Claims] A method for producing a nylon block copolymer, which comprises polymerizing a prepolymer having an oxycarbonyl lactam group at the terminal of formula (I) and a lactam in the presence of a basic lactam polymerization catalyst.