JPS60112825A - Preparation of polyether polyamide block copolymer - Google Patents

Abstract

PURPOSE:To prepare a block copolymer having improved impact resistance and low coloring, by subjecting a polyether prepolymer comprising a polyoxyalkylene as a main component to anionic polymerization. CONSTITUTION:A polyoxyalkylene containing a terminal hydroxyl group is reacted with N-chlorocarbonyl lactam to give a polyether prepolymer. This prepolymer is reacted with lactam in the presence of anionic polymerization catalyst. A polyoxyalkylene having preferably 300-30,000 number-average molecular weight, especially preferably 500-10,000 number-average molecular weight is used as the polyoxyalkylene, and N-Chlorocarbonyl caprolactam, or N-chlorocarbonylpyrrolidinone is used as the N-chlorocarbonyl lactam. An amount of the N-chlorocarbonyl lactam is 1.01-3 equivalents, preferably 10.5-2.2 equivalent based on 2 equivalent hydroxy group in the polyoxyalkylene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a polyether polyamide block combination having excellent impact resistance.

More specifically, the present invention relates to a method for producing an impact-resistant polyether polyamide block copolymer by anionically polymerizing caprolactam in the presence of a prepolymer containing polyoxyalkylene as a main component.

iff 'J A method for producing a polyether polyamide block copolymer containing an oxyalkylene polymer portion and a polylactam polymer portion by anionic polymerization using an anionic polymerization catalyst is disclosed in Japanese Patent Publication No. 54-40120.
No. Publication, U.S. Patent No. 3.862.262, U.S. Patent No. 4,081,
164, 4,084,015 and 4,228,1
12, etc., and it has been shown that this block copolymer can be used for textile fibers, foams, furniture, automobile parts, etc. by taking advantage of its robust properties. One of the main drawbacks of the polyether polyamide flock copolymer obtained by the method of the said patent is that the copolymer is yellow colored. Since the copolymer itself is colored yellow BT, 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 can be obtained.

Further, German Published Patent Application No. 1,909,577 describes that anionic polymerization of lactam can be carried out using an ester of lactam-N-carboxylic acid and a di- or polyol compound as shown in the following formula as an activator.

X However, the purpose of this patent is to produce a 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.

In order to improve the shortcomings of the prior art, the present inventors conducted intensive research on a method for obtaining a polyether polyamide block copolymer which itself is colorless and has excellent properties, and as a result, the present invention was completed. .

That is, by copolymerizing a polyether prepolymer obtained by reacting a polyoxyalkylene having a hydroxyl group at the end with an N-chlorocarbonyl lactam and a lactam in the presence of an anionic polymerization catalyst, it is possible to obtain excellent impact resistance and coloration. This is a method for producing a polyether polyamide block copolymer with a small amount of polyether polyamide.

The polyoxyalkylene having a hydroxyl group at the end used in the method of the present invention is represented by the general formula % (% formula %) (wherein 1 is a divalent hydrocarbon group and nl is an integer of 6 or more), It is a polyol with 2 or more hydroxyl groups in 11 molecules per molecule, and can be compared to 1t1. (i
)H3 -OHz -0kIz -, -011-(lz -, -
(liz -0L(2-CHz -.

(,CLlarel. Specifically, they are polypropylene glycol and polytetramethylene glycol.

The number average molecular weight of this polyoxyalkylene is preferably 800 to 20,000, particularly preferably 500.
~10,000 items are used). Number average molecular weight is 3
If the number average molecular weight is less than 200,001 eAfi, the final 2-polyether polyamide block copolymer will not exhibit sufficient mechanical properties, especially impact strength. Too low.

Therefore, the anionic block polymerization may not be completed (this is not preferable because it may cause some inconvenience).

Examples of the N-chlorocarpollactam used in the method of the present invention include compounds represented by the general formula (in the formula, n] is an integer of 8 to 12), preferably N-
Chlorocarbonylcaprolactam, N-chlorocarbonylpyrrolitinone, and the like can be added.

N-chlorocarbonyl lactam is generally synthesized by reacting latim ether and phosgene in the presence of a tertiary amine, followed by treatment with hydrogen chloride gas.

Self (1)ie Makrotnolekulare
Chemie 127, 34-58 (L'969)) The reaction for obtaining the polyether prepolymer of the present invention, that is, the reaction of a polyoxyalkylene (having a hydroxy group at the end) with N-chlorocarbonyl lactam, is as follows. As shown in the equation, this reaction is further divided into two reactions: dehydrochloric acid reaction and chain extension reaction.
It is thought that this occurs in stages. To illustrate this schematically, the first stage desalting reaction is +I (J) and the second stage chain extension reaction is between
- The amount of polyoxyalkylene and N-chlorocarbonyl lactam in the reaction of chlorocarbonyl lactam is preferably 1.01 to 3 equivalents of N-chlorocarbonyl lactam per 2 equivalents of hydroxyl groups in the polyoxyalkylene. The amount is particularly preferably 1.05 equivalents or more and 2.2 equivalents or less. N-chlorocarbonylcaprolactam is 1.2 equivalents per 2 equivalents of hydroxyl groups in polyoxycalkylene. If the O1 equivalent is less than 11 equivalents, the lactam may not be polymerized or the polymerization time will be extremely long during anionic polymerization of lactam, which is undesirable. It is produced in large quantities and is unfavorable in terms of physical properties.

The reaction temperature in the reaction of the polyoxyalkylene having a hydroxyl group at the terminal and the he-chlorocarbonyl lactam is preferably 0°C or more and 200°C or more, particularly 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 slow, and if it exceeds 200°C, a decomposition reaction will occur, which is not preferable.

For 2 equivalents of hydroxy group in polyoxyalkylene,
If the N-chlorocarbonyl lactam is less than 2 equivalents, 2
In order to carry out the chain extension reaction in the second stage more quickly, an organometallic compound may be used as a catalyst in the second stage reaction. The organometallic compound is preferably a metal salt of a lactam, such as caprolactam magnesium chloride, caprolactam magnesium bromide, caprolactam magnesium iotide, virolidinone magnesium furomide, piperidone magnesium bromide, caprolactam sodium, caprolactam lithium, caprolactam potassium There are compounds such as

When this catalyst is used, the temperature may be 100'C or less, and the reaction is completed in 30 minutes to several hours.

The reaction to obtain the polyether prepolymer can be carried out in the presence or absence of a solvent, and can be carried out in the presence or absence of a dehydrochlorination agent. Examples of the solvent used in this reaction include methylene chloride, chloroform carbon tetrachloride, tetrahydrofuran, dioxane, acetone, methyl ethyl ketone, cyclohexanone, dimethyl sulfoxide, dimethyl cellosolve, diglyme benzene, toluene, xylene, carbon disulfide, etc. Triethylamine, pyridine,
Tertiary amines such as dimethylaniline and diethylaniline can be used, but economically preferred is a method in which the reaction is carried out in the absence of a solvent and a dehydrochlorination agent.

A specific method for copolymerizing the polyether prepolymer synthesized as described above with a lactam is to first mix the polyether prepolymer, lactam, and anionic polymerization catalyst 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 too high, a polymerization reaction will occur during mixing, which is not preferable. The M-containing is carried out by raising the temperature or by pouring it into a heated container or mold. The size of the M-warming box varies depending on the type of lactam, but 5
The temperature is about 0 to 200°C. For example, when ε-caprolactam is used as the lactam, the mixing temperature of the polyether prepolymer, C-caprolactam, and anionic polymerization catalyst is preferably 68 to 100°C, and the polymerization temperature is 100 to 200°C.
°C is preferred. If the temperature is less than 100'C, polymerization is difficult to occur, and if the temperature exceeds 200C, coloration becomes noticeable, which is not preferable.

This polymerization reaction is completed quickly within about 1 hour! do.

In the block copolymerization in the method of the present invention, the amount of polyether prepolymer is 2 to 90% of the total of polyether prepolymer, lactam, and anionic polymerization catalyst.
The weight is 96% by weight, preferably 10 to 80% by weight, and if it is less than 2% by weight, the resulting polyether polyamide block copolymer will not have sufficient impact resistance, and if it exceeds 90% by weight, the strength will decrease, which is not preferred.

The lactam used in the method of the present invention includes lactams such as pyrrolitinone, piperidone, 6-caprolactam, valerolactam, and laurolactam, with ε-caprolactam being particularly preferred.

The amount of lactam is 5-97% by weight, preferably 15-89.7% by weight based on the total of the polyether prepolymer, lactam, and anionic polymerization catalyst.

As the anionic polymerization catalyst used in the method of the present invention, anionic polymerization catalysts generally used for anionic polymerization of lactams can be used. In general, all alkali metals or alkaline earth metals, or their hydrides, halohydrides, alkoxides, oxides,
hydroxide, amide, carbonate, alkyl gold scrap,
It can be used as an alkyl metal halide, a lactam metal, a lactam metal halide, etc., or as a reactant of these with a lactam.

For example, sodium hydroxide, potassium hydroxide, lithium oxide, ethylmagnesium furomide, phenylmagnesium bromide, calcium fluorohydride, strontium carbonate, barium hydroxide, methylsodium, methyllithium, phenylpotassium, diphenylbarium, sodium amide, diethyl Preferred examples include magnesium, magnesium methgicide, caprolactam magnesium bromide, and caprolactam sodium. Also, the amount of anionic polymerization catalyst is 1, tO,l -10mi%, preferably t, and < is o
, a-6i amount% i), 0. L4i% rice flour is not preferred because the anionic block copolymerization will not be completed, and if it exceeds 10% by weight, the strength of the resulting polyether polyamide block copolymer will be low.

Also, the amount of anionic polymerization catalyst is 0.000% relative to the total of polyether prepolymer, lactam, and anionic polymerization catalyst.
1-1OM amount%, preferably 0.3-6N amount%,
If it is less than 0.1% by weight, block copolymerization will not be completed,
If the weight exceeds 6 by 10, the strength of the resulting polyether polyamide block copolymer will decrease, which is not preferable.

The polyether polyamide block copolymer produced by the method of the present invention not only has low impact resistance and heat resistance, but also contains a large amount of polyether prepolymer and can be used as an elastic body. , form, auto f4
It can be used for parts such as L parts and parts of electrical products. The copolymer can be put into the form of conventional molding resins (such as pellets) and then molded into various shapes by injection molding, extrusion or other molding methods, as well as by melting the raw ingredients into ml metallurgy. By polymerizing in a mold, large shapes such as furniture and automobile parts can also be obtained.

The composites can also be used in a variety of applications by adding pigments, dyes, fibers, flame retardants, fillers, plasticizers, stabilizers and other additives.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the Examples.

Example 1 [Synthesis of polyether prepolymer using polypropylene glycol] After purging the 1/round bottom flask equipped with a stirring device with nitrogen, polypropylene glycol (number average molecular weight 2000) was added.
500F and N-chlorocarponylcaprolactam 7
After 7 hours of reaction at 80°, the temperature was reduced to 100° while reducing the pressure with a vacuum pump via an alkali removal tower.
The mixture was further reacted at C for 5 hours. A liquid polyether prepolymer 5459 was obtained.

[Anionic block copolymerization]

Phenylmagnesium bromide 1.52 and ε caprolactam 88.5! The mixed and dissolved mixture of I' and the polyether prepolymer 159 were mixed at 70°C, and the mixture was heated to 140°C.
The mixture was poured into a mold that was heated to . A plate-shaped resin is obtained in a solidification time of 60 seconds, and the resin is white with no coloration, and its physical properties include hardness (Shore D) of 59, impact strength (notched Izod) of 63, 9.c++I/c+++, and flexural modulus. 5
It was 800 Kp/c+1.

Example 2 Caprolactam magnesium bromide 1.5 and ε-
7.59% of the polyether prepolymer synthesized in Example 1 with 41% of caprolactam mixed and dissolved at 70°C.
The mixture was mixed well and poured into a mold heated to 150°C. A white plate-shaped resin is obtained in an assimilation time of 100 seconds, and its physical properties are hardness (Shore D) 81, impact strength (notched Izot) 15, crn/C++11, flexural modulus 1so
oo It was immediately divalent.

Comparative Example 1 Caprolactam magnesium bromide 1.5y- and ε
- Mixed and dissolved caprolactam 489 and Example 1
Polyether prepolymer 0.57 synthesized at 70℃
The mixture was mixed well and poured into a mold heated to 140°C, but no polymerization occurred even after 1 hour.

Comparative Example 2 Caprolactam magnesium bromide 1.57 and ε-
The polyether prepolymer 467 synthesized in Example 1 was mixed well with a mixture of caprolactam 2.57 at 7°C and poured into a mold heated to 140°C, but the mixture became cloudy. It just didn't solidify.

Examples 3-5. Comparative Example 3 100rn1. equipped with a stirring device. Polypropylene glycol (number average molecular weight 1000) 509 in a round bottom flask
Then, the amount of N-chlorocarbonylcabrolactam shown in Table 1 was charged and reacted at 90°C for 5 hours, and then further reacted at 110°C for 8 hours while applying reduced pressure with a vacuum pump via an alkali removal tower. and synthesized a boroether prepolymer. A mixed solution of caprolactam magnesium bromide 1.57 and ε-caprolactam 88.5F was combined with the polyether prepolymer 15P shown in Table 1 at 70°C, and a mold was heated to 140°C. and polymerized. The solidification time and properties of the polyether polyamide block copolymer obtained are shown in Table 1.

Example 6 [Synthesis of polyether prepolymer using polytetramethylene glycol] After purging a 500 mm round bottom flask equipped with a stirring device with nitrogen, polytetramethylene glycol (number average molecular weight
ooo ) aoo and N-chlorocarbonylcaprolactam 85P are charged and reacted at 70°C for 10 hours, and then further reacted at 100°C for 5 hours while reducing the pressure with a pump after passing through an alkali removal tower. 815 pieces of liquid polyether prepolymer were obtained.

[Anionic block copolymerization]

Phenylmagnesium bromide 1.5 F (!:ε
- A mixed solution of caprolactam 88.5S' and the polyether prepolymer 1O) were mixed at 80°C and poured into a mold heated to 150°C. Solidification time 5
A white plate-shaped resin was obtained in minutes, and its physical properties were a hardness (Shore D) of 78, an impact strength of 22 hanlon, and a flexural modulus of 8,800 i/d.

Example 7 [Synthesis of polyether prepolymer] After purging a 100-mm round bottom flask equipped with a stirring device with nitrogen, polypropylene glycol (MI
ooo ) 509. 5.87% of N-chlorocarbonylcaprolactam and 47% of dimethylaniline were charged and reacted at 25°C for 1 hour. After washing and removing the generated dimethylaniline sulfate with a methylene chloride-water system, the methylene chloride layer was concentrated and Ether prepolymer 49
I got 2.

[Anionic block copolymerization]

Phenylmagnesium furomite 1.5 F/-(!:
A mixed solution of E-caprolactam 38.55' and the polyether prepolymer 1O1 were mixed at 80°C, and the mixture was poured into a mold heated to 150°C. A white plate-shaped resin was obtained in a solidification time of 80 seconds, and its physical properties were hard! i(
Shore D) 71. Impact resistance strength 24 kcmlon,
The flexural modulus was 9600/d.

Examples 8 to 11 Polypropylene glycol (number average molecular weight 2000) 505' and N-chlorocarbonylcaprolactam 61P were charged into a 100 m round spoon flask equipped with a stirrer, and after reacting at 90°C for 5 hours, an alkali removal tower was added. The reaction was further carried out at 110° C. for 3 hours while reducing the pressure using a vacuum pump. Thereafter, while maintaining the temperature at 70°C, nine anionic catalysts of the types shown in Table 2 were added and reacted for 8 hours to synthesize an IIP IJ ether prepolymer.

Caprolactam magnesium bromide 19 and ε-caprolactam 34 g were mixed and dissolved, and the above polyether prepolymer 15P was mixed at 80°C, heated to 150°C, poured into a mold, and polymerized. The solidification time and properties of the polyether polyamide block copolymer obtained are shown in Table 2.

Example 12 A mixed solution of caprolactam magnesium prolide ly and ε-caprolactam 247 and the polyether prepolymer 25F synthesized in Example 1 were mixed well at 70°C and poured into a mold heated to 140°C. did. After an assimilation time of 70 seconds, a white translucent plate-shaped resin was obtained, and its physical properties were measured for hardness (Shore 1) of 29 and impact strength (notched isod), but it did not break.

Claims (1)

[Claims] A polyether polyamide block copolymer characterized in that a polyether prepolymer obtained by reacting a polyoxyalkylene having a hydroxyl group at the end with N-chlorocarbonyl lactam and a lactam are copolymerized in the presence of an anionic polymerization catalyst. manufacturing method.