JPH0119810B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a star block copolymer with excellent impact resistance and a method for producing the same. More specifically, it relates to a star block copolymer consisting of a star polyether part and a polyamide part, which is obtained by anionically polymerizing a lactam in the presence of a polyether prepolymer mainly composed of star polyoxyalkylene, and a method for producing the same. . 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. In addition, in these production methods, a bifunctional acyllactam compound is used as a chain extender, so when the chain extender is reacted with a star-shaped polyoxyalkylene having three or more hydroxy groups in one molecule, a network It is not possible to create a structure and synthesize the desired star block copolymer. 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 star block copolymer of a star polyoxyalkylene and a polyamide like the method of the present invention. As a result of extensive research into star block copolymers with excellent mechanical properties and good hue, the present inventors found that the general formula (In the formula, R ¹ is a trivalent to hexavalent alcohol residue, R ² is an aliphatic hydrocarbon residue having 2 to 6 carbon atoms, R ¹ − [(R ²
-O) _-o ] The average molecular weight of _{the p-} corresponding portion is 300 to 50,000,
R ³ is a carbon number, 1 to 12 aliphatic hydrocarbon residues, R ⁴
is an aliphatic hydrocarbon residue having 3 to 12 carbon atoms, n×p is 7 to 1000, (m+1)×p is 25 to 310, k is 1 or 0, and p is 3 to 6). They discovered this polymer and completed the present invention. That is, the general formula (In the formula, R ¹ is a trivalent to hexavalent alcohol residue, R ² is an aliphatic hydrocarbon residue having 2 to 6 carbon atoms, R ¹ −[(O
−R ² ) − _o ] The average molecular weight of _{the p-} corresponding portion is 300 to 50,000,
R ³ is a carbon number, 1 to 12 aliphatic hydrocarbon residues, R ⁴
is an aliphatic hydrocarbon residue having 3 to 12 carbon atoms, n×p is 7 to 1000, (m+1)×p is 25 to 310, k is 1 or 0, and p is 3 to 6). In a method for producing a polymer, a star polyether prepolymer obtained by reacting a star polyoxyalkylene having 3 to 6 hydroxy groups at the terminal with N-chlorocarbonyl lactam and a lactam are mixed in the presence of an anionic polymerization catalyst. This is a method for producing a star block copolymer with excellent physical properties and little coloration by copolymerizing with . The star polyoxyalkylene having three or more hydroxy groups at the terminals used in the method of the present invention has the general formula R ¹ −[(R ² −O))− _o H] _p (wherein R ¹ is 3 to 6 ^R2 is an aliphatic hydrocarbon residue, P is 3 to 6), and is a polyol having 3 to 6 hydroxy groups in one molecule, and ^R2 is preferably A hydrocarbon residue having 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, such as -CH ₂ -CH ₂ -,

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

[Synthesis of star-shaped polyether prepolymer]

After purging a round-bottomed flask with a stirring device with nitrogen, 500 g of triol-type star-shaped polypropylene glycol derived from trimethylolpropane (manufactured by Wako Pure Chemical Industries, Ltd., polypropylene glycol molecular weight 3000 (triol type)) and N were added.
-Prepare 88g of chlorocarbonyl caprolactam
After reacting at 80°C for 7 hours, the mixture was reacted at 100°C for 5 hours while reducing the pressure with a vacuum pump. 549 g of liquid star-shaped polyether prepolymer was obtained. Examples 1-4 Caprolactam magnesium bromide 1.5g
and Reference Example 1 containing ε-caprolactam in the amount shown in Table 1 and the amount shown in Table 1.
The star-shaped polyether prepolymer synthesized above was mixed at 70°C and poured into a mold heated to 140°C. At the solidification times shown in Table 1,
A plate-shaped resin with little coloring was obtained. Their physical properties are shown in Table 1.

[Table] Examples 5 to 7 The anionic polymerization catalyst of the type and amount shown in Table 2 and the amount of ε-caprolactam shown in Table 2 were mixed and degassed, and the mixture synthesized in Reference Example 1 was used. 15 g of star-shaped polyether prepolymer were mixed at 80°C and poured into a mold heated to 140°C. Platy resins with little coloring were obtained at the solidification times shown in Table 2. Their physical properties are shown in Table 2.

[Synthesis of star-shaped polyether prepolymer]

34g of pentaerythritol and potassium hydroxide
16 g of a 50 wt% aqueous solution and 300 g of toluene were placed in a pressurized container, and water was removed by azeotropy with toluene to eliminate toluene. 891 g of propylene oxide was gradually added to the residue while cooling it in a nitrogen gas atmosphere to maintain the temperature at 105-110°C. Thereafter, the mixture was kept at 105 to 110°C and reacted for further 3 hours. The product was neutralized with dilute sulfuric acid and washed several times with distilled water to obtain 910 g of tetraol type star polypropylene glycol having an average molecular weight of 3,700.
After purging a 200 ml round bottom flask equipped with a stirring device with nitrogen, 100 g of the above-mentioned tetraol-type star polypropylene glycol derived from pentaerythritol and 17.6 g of N-chlorocarbonylcaprolactam were charged and reacted at 80°C for 10 hours. The mixture was reacted at 100° C. for 5 hours while reducing the pressure with a vacuum pump. 110 g of liquid star-shaped polyether prepolymer were obtained. Examples 8 to 9 Reference Example 2: Mixing and dissolving the anionic polymerization catalyst of the type and amount shown in Table 3 and the amount of ε-caprolactam shown in Table 3, and the amount shown in Table 3
The star-shaped polyether prepolymer synthesized above was mixed at 70°C and poured into a mold heated to 150°C. At the solidification times shown in Table 3, respectively,
A plate-shaped resin was obtained. Their physical properties are shown in Table 3.

[Synthesis of star-shaped polyether prepolymer]

22.8 g of sorbitol, 16 g of a 50 wt% aqueous solution of potassium hydroxide, and 300 g of toluene were placed in a pressurized container, and water was removed by azeotropy with toluene, and the toluene was also expelled. Add 977g of propylene oxide to the residue while cooling it in a nitrogen gas atmosphere to maintain a temperature of 105-110℃.
was added gradually. Then keep it at 105-110℃ 3
The reaction was allowed to proceed for additional time. After neutralizing the product with dilute sulfuric acid, it was further washed several times with distilled water to obtain an average molecular weight of 8000.
989 g of hexaol type star polypropylene glycol was obtained. After purging a 200 ml round bottom flask equipped with a stirring device with nitrogen, 100 g of the hexaol-type star polypropylene glycol derived from sorbitol and 13.3 g of N-chlorocarbonylcaprolactam were charged and reacted at 80°C for 10 hours. The reaction was carried out at 100° C. for 5 hours while reducing the pressure with a vacuum pump. 109 g of liquid star-shaped polyether prepolymer was obtained. Example 10 A mixed solution of 2 g of caprolactam magnesium bromide and 38 g of ε-caprolactam,
10 g of the star-shaped polyether prepolymer synthesized in Reference Example 3 was mixed at 70°C and poured into a mold heated to 160°C. A plate-shaped resin was obtained in a solidification time of 95 seconds, and its physical properties were 74 in hardness (Shor D) and 73.5 Kg·cm/cm in impact strength (Notched Izod). Example 11 Caprolactam magnesium bromide 1.5g
A mixed solution of 38.5 g of ε-caprolactam and 10 g of the star-shaped polyether prepolymer synthesized in Reference Example 1 were mixed at 80°C, and the mixture was poured into a mold heated to 160°C. A plate-shaped resin is obtained in a solidification time of 110 seconds, and its physical properties are hardened (Shor D)
72, Impact resistance strength (Izod with notch) 66.0Kg・
It was cm/cm.

Claims (1)

[Claims] 1. General formula (In the formula, R ¹ is a trivalent to hexavalent alcohol residue, R ² is an aliphatic hydrocarbon residue having 2 to 6 carbon atoms, R ¹ − [(R ² − O) − _o ] the average of the portion corresponding to _p molecular weight
300 to 50,000, R ³ is an aliphatic hydrocarbon residue having 1 to 12 carbon atoms, R ⁴ is an aliphatic hydrocarbon residue having 3 to 12 carbon atoms, n×p is 7 to 1000, (m+1)×p is 25-310, k represents 1 or 0, and p represents 3-6. ) A star block copolymer represented by 2 General formula (In the formula, R ¹ is a trivalent to hexavalent alcohol residue, R ² is an aliphatic hydrocarbon residue having 2 to 6 carbon atoms, R ¹ − [(R ² − O) − _o ] the average of the portion corresponding to _p molecular weight
300 to 50,000, R ³ is an aliphatic hydrocarbon residue having 1 to 12 carbon atoms, R ⁴ is an aliphatic hydrocarbon residue having 3 to 12 carbon atoms, n×p is 7 to 1000, (m+1)×p is 25-310, k represents 1 or 0, and p represents 3-6. ) In the method for producing a star block copolymer represented by A method for producing a star block copolymer, which comprises copolymerizing a lactam in the presence of an anionic polymerization catalyst.