JPS60170624A - Preparation of polyether ester amide - Google Patents

Abstract

PURPOSE:To obtain the titled amide having improved hue and melt transparency, by polycondensing a carboxy-terminated amide propolymer with a poly(alkylene oxide)glycol in the molten state in the presence of an organotin compound. CONSTITUTION:(A) A dicarboxylpolyamide prepolymer having terminal carboxyl groups, optimally 500-5,000mol.wt. is polycondensed with (B) a poly(alkylene oxide)glycol, optimally poly(tetramethylene oxide)glycol in the molten state in the presence of an organotin compound, optimally monobutylmonohydroxytin oxide, in an amount of 0.01-0.2wt% expressed in terms of tin atoms based on the polyether ester as a catalyst. EFFECT:A polyamide with a low gel content is obtained in a short time.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyetheresteramides.

Polyether ester amide is well known, and its manufacturing method includes a method in which a carboquino-terminated amide prepolymer and poly(alkylenoxide) glycol are subjected to a polycondensation reaction in a molten state (Japanese Unexamined Patent Publication No. 159586/1986 and Japanese Unexamined Patent Publication No. 159586). Publication No. 54-47798).

These methods use the general formula T 1 (OR,
) titanotetraalkoxide represented by 4, Z r
This method uses zirconium or hafnium tetraalkoxide such as (OR) 4 and Hf (OR) 4, and is intended to obtain a polyether ester amide with a high degree of polymerization and excellent color tone.

However, as the amount of titanium, zirconium, and hafnium-based catalysts increases, their activity increases and they are effective in shortening polymerization time, but they also generate gel-like foreign substances and cause a decrease in color tone from yellow to grayish brown. This causes problems such as increased haze of the polymer. Therefore, the above-mentioned method is not necessarily a satisfactory method because it cannot be used by adding in a large amount, and the polymerization property (polymerization rate and degree of polymerization achieved) is not sufficient with a small amount.

The present inventors investigated a polycondensation catalyst that does not involve problems such as gelation, decreased color tone, and increased haze in the polycondensation reaction of polyether ester amide, and can produce a polymer with a high degree of polymerization in a short time. invention has been achieved.

That is, the present invention provides a method for producing a polyether ester amide segment copolymer by polycondensing a dicarboxyl polyamide prepolymer having carboxyl groups at both ends and poly(alkylene oxide) glycol in a molten state. Provided is a method for producing polyetheresteramide, characterized in that the condensation reaction is carried out in the presence of an organotin compound.

The method of the present invention will be specifically described below.

Examples of the organotin compound used as a polycondensation catalyst in the method of the present invention include monoalkyltin compound, monoaryltin compound, dialkyltin compound, diaryltin compound, trialkyltin compound, triaryltin compound. , tetraalkyltin compounds, etc. are used. Among these are monoalkyl or monoaryltin compounds such as monobutyl monohydroxytin oxide, monobutyltin triacetate, monobutyltin monooctylate, monobutyltin monoacetate, monophenyltin triacetate, and dibutyltin oxide, dibutyltin dichloride, dibutyltin dilaurate. , dibutyltin maleate, dibutyltin diacetate, diphenyltin oxide, and other dialkyl or diaryltin compounds are effective and preferably used. The amount of tin (added in the blend) is preferably 0.02 to 0.5 M% by weight, more preferably 0.01 to 0.2% by weight, based on the amount of tin atoms based on the polyetherester.

The polycondensation catalyst according to the present invention is not applicable when it is added to a polycondensation reaction system of a dicarboxyl polyamide prepolymer and poly(alkylene oxide) glycol in a molten state, and is added at the stage of producing the prepolymer. .

The dicarboxyl polyamide prepolymer having carboxyl groups at both ends used in the production of the polyether ester amide segment copolymer of the present invention includes lactam,
one or more amide-forming monomer units, such as a salt of an ω-aminocarboxylic acid or a dicarboxylic acid and a diamine;
It can be synthesized by reacting a dicarboxylic acid having 4 to 2.0 carbon atoms under normal polyamide polymerization reaction conditions.

For example, lactams such as caprolactam, enantlactam, dodecalactam (laurolactam), undecanolactam, ω-aminocarboxylic acids with aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, nylon-66, -69, - 610, -612, -1
A nylon salt, which is a precursor such as 16, -126, and a dicarboxylic acid having 4 to 20 carbon atoms are pressurized at a temperature of 230 to 300°C in the presence or absence of water, at normal pressure or N2.
By reacting under flow, a polyamide prepolymer substantially having carboxyl groups at both ends can be prepared. The dicarboxylic acids having 4 to 20 carbon atoms used here are aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipinoic acid, pimelic acid, speric acid, azelaic acid, sepadinoic acid, undecanodic acid, and dodecanedioic acid, terephthalic acid, and isophthalic acid. acids, aromatic dicarboxylic acids such as phthalic acid and natutalenodicarboxylic acid, and alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and dicyclohexyl-4,4'-dicarboxylic acid, and the amount used is It is used in substantially the same molar amount as the poly(alkylene oxide) glycol or in a slightly excess amount. The molecular weight of the carboxy-terminated polyamide prepolymer is 300-10.00
0, more preferably 500 to 5,000, but for the purpose of controlling blocking properties, the entire amount of the dicarboxylic acid component is not used in the prepolymer synthesis step, but a portion is used in the polycondensation step with poly(alkylene oxide) glycol. Variations are also possible.

The most preferred combination of raw materials for the polyamide prepolymer is as follows. That is, caprolactam, laurolactam, 12-
Aminododecanoic acid, 11-aminoundecanoic acid, nylon 66 salt, 612 salt, and 116 salt were used, and the dicarboxylic acid was selected from terephthalic acid, isophthalic acid, adipic acid, sepadino acid, and dodecanedioic acid. be.

Poly(alkylene oxide) glycol, which is another component in the polyether ester amide polycondensation of the present invention, includes polyethylene glycol, poly(1,2- and 1,3-propylene oxide) glycol, poly(
Examples include tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, block or random copolymers of ethylene oxide and propylene oxide, block or random copolymers of ethylene oxide and tetrahydrofuran, among others, which have excellent heat resistance, water resistance, and mechanical properties. Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as physical strength and elastic recovery. The number average molecular weight of poly(alkylene oxide) glycol is 300-6
．． 000, but a molecular weight range is selected that does not cause coarse phase separation during polymerization and has excellent low-temperature properties and mechanical properties.

The polycondensation reaction of the polyether ester amide segment copolymer is carried out by heating the aforementioned dicarboxy-terminated polyamide prepolymer and poly(alkylene oxide) glycol to a molten state, that is, to a temperature above the melting point of both, and reacting with stirring in the presence of a catalyst. This is achieved by The temperature of polycondensation is 180-300°C, preferably 230-200°C.
It can be carried out at 80°C. In addition, in order to efficiently generate ester bonds, it is important to conduct the reaction system in a vacuum system of 50 R1Hg or less, more preferably 5*gHg or less, or under atmospheric pressure and N2 gas flow to distill the condensed water out of the system. .

The reaction time is usually 10 minutes to 10 hours, preferably 1 to 5 hours. The reaction time varies depending mainly on the type of poly(alkylene oxide) glycol and the copolymerization composition ratio, but it must be a time that increases the degree of polymerization to a degree suitable for the elastomer material for molding, which is the object of the present invention.

The degree of polymerization varies depending on the copolymer composition, but the number average molecular weight is approximately 15.000 or more, more preferably 20,
OOO~30. It's OOO.

The method for polymerizing polyether ester amide of the present invention can be used over almost the entire range of copolymerization composition ratios, but from a practical standpoint, the ratio of polyamide to polyether ester is 9.
It can be effectively used in a range of 5 to 10% by weight to 5 to 90% by weight.

In the method for polymerizing the polyether ester amide segment copolymer of the present invention, a heat-resistant and light-resistant stabilizer such as an acid release inhibitor, a thermal decomposition inhibitor, and an ultraviolet absorber can be added before or after polymerization. In addition, in order to improve the properties of the product, depending on the use and purpose, hydrolysis resistance improvers, coloring agents (pigments, dyes), antistatic agents, conductive agents, flame retardants, reinforcing materials, fillers, lubricants, nucleating agents. , a mold release agent, a plasticizer, an adhesion aid, an adhesive, etc. can be optionally contained.

The method of the present invention exhibits the following effects.

(11 Polyetheresteramide with a high degree of polymerization can be obtained in a short time.

(2) The color tone of the obtained polyether ester amide is good.

(3) Similarly, melt transparency is excellent.

(4) A polyether ester amide with less gel can be obtained.

The present invention will be explained below with reference to Examples. In the examples, unless otherwise specified, parts mean parts by weight.

Example 1 N-1, which is carboxyl-arranged at both ends, by ring-opening polycondensation of laurolactam in the presence of dodecadionic acid.
2 prepolymers were obtained. This prepolymer was subjected to terminal group determination according to the usual nylon end group determination method, and it was confirmed that the prepolymer contained carboxyl groups at both ends with almost no amino end. 60.0 parts of the dicarboquine-terminated N-12 prepolymer having a number average molecular weight of 975 thus prepared and 40.0 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 650 were added to 1 kg of monobutyl monohydroxytin (5.03 parts). (0.017% by weight per polymer as the amount of tin atoms) and the acid distribution inhibitor Ilkanox 1098 (N,N'-hexamethylenenobis(3,5
- Di-t-butyl-4-hydroxy-hydronnamy F')) 0.2 part was charged into a reaction vessel equipped with a helical ribbon stirring blade, purged with N2, and heated and stirred at 220°C for 15 minutes to obtain a homogeneous product. After obtaining a clear solution, it was heated to 250 °C for 60 min according to the temperature increase and pressure reduction program, (l WNHg
polymerization conditions. When the reaction was carried out under these conditions for 2 hours and 10 minutes, the reaction rate at 22 rpm was 8. (A viscous colorless and transparent molten polymer with a stirring torque of J#.0 was obtained, and when this polymer was discharged into water as a gaunt, one crystal formed and became white.

The polyether ester amide thus obtained has a relative viscosity (ηr) of 1.95 measured in orthochlorophenol at 25°C at a concentration of 0.5%, and has a relative viscosity of 2160 f M
, the melt index measured at 230°C was 4.51.
/ It was 10 minutes. This viscosity level was high enough for extrusion molding of tubes, etc., and also allowed blow molding by adjusting the molding temperature.

A monofilament with a diameter of about 0.1 yd was taken from the melt-inodexo and observed under a microscope to determine how many gels were contained in 50 parts M, but no gel was found.

Pellets were sorted and arranged by press molding, and their mechanical properties were measured according to ASTM standards.

Tensile modulus 1.300 kq/cd hardness
54D Tensile strength at break 720 kg/d Elongation 850% Example 2.3, Comparative Examples 1 to 7 Exactly the same conditions as in Example 1 except for changing the type and amount of the catalyst (monobutyl monohydroxytin oxide) added Polycondensation was carried out using the method, and the polymerizability and polymer properties were evaluated. The results are shown in Table 1.

Example 4, Comparative Example, 8,9 55 parts of dicarboxyl N-6 prepolymer (average molecular weight 1,050) prepared in advance by polycondensing ε-caprolactam in the presence of adipinoic acid and number average molecular weight 1
．． 000 poly(alkylene oxide) glycol 50
A polyether ester amide was prepared under the same polymerization conditions as in Example 1, except that 50% of the polyether ester amide was used. At this time, during polymerization 5.0
A portion of caprolactam was distilled out of the system.

For comparison, the polymerization catalyst was changed from monobutyl monohydroquine tin oxide to tetrabutyl titanate and tetrabutyl zirconate.

The evaluation results of polymerizability and polymer properties are also listed in Table 1.

Example 5 A polycondensation reaction was carried out under exactly the same polymerization conditions as in Example 1 except that 0.05 part of monobutyl monohydroxytin oxide was used instead of monobutyl monohydroxytin oxide. The predetermined torque was reached in a polymerization time of 2 hours and 45 minutes, and a colorless and transparent polymer with ηr of 1.97 was obtained when melted. Moreover, no gel was generated at all.

Example 6 A polycondensation reaction was carried out under exactly the same conditions as in Example 1 except that 0.10 part of dibutyltin oxide was used instead of monobutyl monohydroxytin oxide. The predetermined torque was reached in 3 hours and 20 minutes of polymerization time, and ηr was 1.94.
A colorless and transparent polymer was obtained when melted. Also, Kel was not included at all.

Patent applicant Higashi Shikikai Co., Ltd.

Claims (1)

[Claims] In a method for producing a polyether ester amide segment copolymer by subjecting a dicarboquine polyamide prepolymer having carboxyl groups at both ends to a polycondensation reaction in a molten state and poly(alkylenooxide) glycol, the polycondensation reaction 1. A method for producing polyether ester amide, characterized in that the step is carried out in the presence of an organic tin compound.