JPS6363566B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a polyether polyamide block copolymer 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. A method for producing a polyether polyamide block copolymer containing a polyoxyalkylene polymer portion and a polylactam polymer portion by anionic polymerization using an anionic polymerization catalyst is disclosed in Japanese Patent Publication No. 1982-40120, U.S. Pat. No. 3,862,262,
4031164, 4034015, and 4223112, and 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 polyether polyamide block copolymers obtained by the method of the patent is that the copolymers are 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. Further, German Published Patent Application No. 1909577 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. (In the formula, R is an aliphatic group having 2 to 12 carbon atoms, m is 4 to
(an integer of 12) However, the purpose of this patent is to produce a polyamide by homopolymerization of a 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 made 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, a colored product with excellent impact resistance is produced. This is a method for producing a polyether polyamide block copolymer with a small amount of polyether. The polyoxyalkylene having a hydroxy group at the terminal used in the method of the present invention has the general formula HO(-R ¹ -O)-nH (where R ¹ is a divalent hydrocarbon group and n is 6
is a polyol having two or more hydroxy groups in one molecule, and R ¹ is, for example, -
CH ₂ −CH ₂ −,

[Formula] −CH ₂ −CH ₂ −CH ₂ −, −CH ₂ −CH ₂ −CH ₂ −CH ₂ −,

Examples include [Formula]. Specifically, they are polypropylene glycol and polytetramethylene glycol. The number average molecular weight of this polyoxyalkylene is preferably 300 to 20,000, particularly preferably 500.
~10000 are used. Number average molecular weight is 300
If the number average molecular weight is less than 20,000, the final polyether polyamide block copolymer will not have sufficient mechanical properties, especially impact strength, and if the number average molecular weight exceeds 20,000, the terminal hydroxyl group concentration of the polyoxyalkylene will be too low, resulting in anion This is not preferred because it causes problems such as incomplete block polymerization. The N-chlorocarbonyl lactam used in the method of the present invention has the general formula (In the formula, m is an integer of 3 or more and 12 or less) Preferably, N-chlorocarbonylcaprolactam, N-
Examples include chlorocarbonylpyrrolidinone. N-chlorocarbonyl lactam is generally synthesized by reacting lactam ether and phosgene in the presence of a tertiary amine, followed by treatment with hydrogen chloride gas. (Die Makromolekulare Chemie 127 , 34−
53 (1969)) The reaction for obtaining the polyether prepolymer of the present invention, that is, the reaction between a polyoxyalkylene having a hydroxyl group at the end and N-chlorocarbonyl lactam, is thought to occur as shown in the following formula. (In the formula, l is an integer greater than or equal to 0, ^R2 is ( _-CH2 ) _-n , ^R3
is -NH- ^R2- or ^-R2 -NH-, k is 0 or 1, and these may be mixed in one molecule. ) This reaction further involves two reactions: dehydrochlorination reaction and chain extension reaction.
It is thought to occur in stages. To illustrate this schematically, the first stage desalination reaction is As the second chain extension reaction, and further

[Synthesis of polyether prepolymer using polypropylene glycol]

After purging a round bottom flask with a stirring device with nitrogen, 500 g of polypropylene glycol (number average molecular weight 2000) and 70 g of N-chlorocarbonylcaprolactam were charged and reacted at 80°C for 7 hours, then passed through an alkali removal tower. The mixture was further reacted at 100°C for 5 hours while reducing the pressure using a vacuum pump.
545 g of liquid polyether prepolymer was obtained. [Anionic block copolymerization] A mixed solution of 1.5 g of phenylmagnesium bromide and 33.5 g of ε-caprolactam was mixed with 15 g of the polyether prepolymer at 70°C.
The mixture was poured into a mold heated to 140°C. Solidification time
A plate-shaped resin is obtained in 60 seconds, and the resin is white with no coloring, and its physical properties include hardness (Shor D) of 59, impact strength (notched Izod) of 63 kg/cm/cm, and flexural modulus of 5800 kg/cm ² It was hot. Example 2 Caprolactam magnesium bromide 1.5g
A mixture of 41 g of ε-caprolactam and the polyether prepolymer synthesized in Example 1
7.5g was mixed well at 70°C and poured into a mold heated to 150°C. A white plate-shaped resin was obtained in a solidification time of 100 seconds, and its physical properties were hardness (Shor D) of 81,
Impact resistance strength (Izotsud with notches) 15Kgcm/cm,
The flexural modulus was 18000 Kg/cm ² . Comparative example 1 Caprolactam magnesium bromide 1.5g
A mixture of 48 g of ε-caprolactam and the polyether prepolymer synthesized in Example 1
0.5 g was mixed well at 70°C and poured into a mold heated to 140°C, but no polymerization occurred even after 1 hour. Comparative example 2 Caprolactam magnesium bromide 1.5g
and ε-caprolactam 2.5g in Example 1.
46g of polyether prepolymer synthesized at 70℃
The mixture was mixed well and poured into a mold heated to 140°C, but the mixture only became cloudy and did not solidify. Examples 3 to 5, Comparative Example 3 50 g of polypropylene glycol (number average molecular weight 1000) was placed in a 100 ml round bottom flask equipped with a stirring device.
Then, the amount of N-chlorocarbonylcaprolactam shown in Table 1 was charged and reacted at 90°C for 5 hours, and then further reacted at 110°C for 3 hours while reducing the pressure with a vacuum pump via an alkali removal tower.
A polyether prepolymer was synthesized. A mixture of 1.5 g of caprolactam magnesium bromide and 33.5 g of ε-caprolactam and 15 g of the polyether prepolymer shown in Table 1 were added to the
Mix at ℃ and inject into a mold heated to 140℃,
Polymerized. Table 1 shows the solidification time and the properties of the polyether polyamide block copolymer obtained.

[Synthesis of polyether prepolymer using polytetramethylene glycol]

After purging a 500 ml round bottom flask with a stirring device with nitrogen, 300 g of polytetramethylene glycol (number average molecular weight 3000) and 35 g of N-chlorocarbonylcaprolactam were charged and reacted at 70°C for 10 hours. The reaction was continued at 100°C for 5 hours while reducing the pressure using a vacuum pump. 315g liquid polyether prepolymer
was gotten. [Anion block copolymerization] 1.5 g of phenylmagnesium bromide and ε-
A mixed solution of 38.5 g of caprolactam and 10 g of the polyether prepolymer 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 5 minutes, and its physical properties were a hardness (shear D) of 73, an impact strength of 22 Kg/cm, and a flexural modulus of 8800 Kg/ ^cm2 . Example 7 [Synthesis of polyether prepolymer] After purging a 100 ml round bottom flask equipped with a stirring device with nitrogen, 50 g of polypropylene glycol (number average molecular weight 3000), 5.8 g of N-chlorocarbonylcaprolactam and 4 g of dimethylaniline were charged. The reaction was carried out at ℃ for 10 hours. After the generated dimethylaniline hydrochloride was removed by washing with a methylene chloride-water system, the methylene chloride layer was concentrated to obtain 49 g of polyether prepolymer. [Anion block copolymerization] 1.5 g of phenylmagnesium bromide and ε-
A mixed solution of 38.5 g of caprolactam and 10 g of the polyether prepolymer 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 a hardness (Shor D) of 71, an impact strength of 24 Kg/cm, and a flexural modulus of 9600 Kg/ ^cm2 . Examples 8-11 50 g of polypropylene glycol (number average molecular weight 2000) was placed in a 100 ml round bottom flask equipped with a stirring device.
and 61g of N-chlorocarbonylcaprolactam
After reacting at 90℃ for 5 hours, it was heated to 110℃ while reducing the pressure with a vacuum pump via an alkali removal tower.
The reaction was further carried out at ℃ for 3 hours. Then another 70℃
Anionic catalysts of the type and amount shown in Table 2 were added while maintaining the temperature, and the mixture was reacted for 3 hours to synthesize a polyether prepolymer. A mixed solution of 1 g of caprolactam magnesium bromide and 34 g of ε-caprolactam and 15 g of the polyether prepolymer were mixed at 80°C, and the mixture was poured into a mold heated to 150°C and polymerized. The solidification time and properties of the polyether polyamide block copolymer obtained are shown in Table 2.

[Table] Example 12 A mixed solution of 1 g of caprolactam magnesium bromide and 24 g of ε-caprolactam and 25 g of the polyether prepolymer synthesized in Example 1
were mixed well at 70°C and poured into a mold heated to 140°C. A white translucent plate-shaped resin was obtained in a solidification time of 70 seconds, and its physical properties were measured for hardness (Shor D) of 29 and impact strength (notched Izod), but did not break.

Claims (1)

[Claims] 1. A polyether polyamide block copolymer characterized in that a polyether prepolymer obtained by reacting a polyoxyalkylene having a hydroxyl group at the end with an N-chlorocarbonyl lactam and a lactam are copolymerized in the presence of an anionic polymerization catalyst. manufacturing method.