JPS62283125A - Production of polyester polyamide block copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having excellent heat-resistance, processability, transparency and mechanical strength and suitable for molded article, film, etc., by reacting an aromatic polyester block with a bifunctional carboxylic acid (halide) and an amine. CONSTITUTION:(A) A block of formula III (Ar is aromatic residue; Ar' is phenol residue) is produced by dissolving (i) a bifunctional aromatic carboxylic acid (halide) (e.g. the compound of formula) in an organic solvent (e.g. methylene chloride) and mixing and reacting the solution with another solution produced by dissolving (ii) a bifunctional phenol (e.g. the compound of formula II) in an alkaline aqueous solution. The block A is converted to a block of formula IV (R<1> and R<2> are 1-12C alkylene) by mixing and reacting with (B) (i) an organic solvent solution of an aliphatic dicarboxylic acid (halide) and (ii) an alkaline aqueous solution of an aliphatic diamine. The objective copolymer composed of the components A and B at an A/B ratio of 95/5-5/95 can be produced by this process.

Description

DETAILED DESCRIPTION OF THE INVENTION a. Field of Industrial Application The present invention relates to a method for producing a polyester-polyamide plotter copolymer which is composed of aromatic polyester units and aliphatic polyamide units and has excellent heat resistance and moldability.

b. Prior Art Aromatic polyester resins obtained by condensation polymerization of aromatic dicarboxylic acid halides and difunctional phenols are widely used as resins with high heat resistance in various molded products. However, although the aromatic polyester resin has the advantage of high heat resistance, it also has the disadvantage of poor moldability.

On the other hand, although polyamide resin has a low melting point and poor moldability, it has the drawback of extremely low heat resistance compared to the aromatic polyester resin.

Further, JP-A-58-147420 discloses an aromatic polyester amide random copolymer prepared by reacting an aromatic diamine, a dihydric phenol, and an aromatic dibasic acid sybaride. However, although the aromatic polyester amide random copolymer has been improved in its moldability, the molding temperature is high and it is still insufficient for practical use.

Problems to be Solved by the C0 Invention The inventors of the present invention aim to improve such molding processability and obtain a resin with excellent thermal stability and heat resistance (as a result of intensive studies,
The inventors have found that the above-mentioned problems can be solved by creating a block copolymer containing aromatic polyester units and polyamide units in a specific ratio, and have arrived at the present invention based on these findings.

d. Means for solving the problem, that is, the present invention provides (Δ) a bifunctional aromatic carboxylic acid represented by the general formula 110-C-Ar-C-OH or an acid halide of the carboxylic acid; (B) Acid of the general formula or the carboxylic acid is condensed and polymerized with a difunctional phenol represented by the general formula 10-Ar'-OH to produce an aromatic polyester having a repeating unit represented by the general formula. An acid halide and a difunctional amine represented by the general formula 11□N-R''-Nl+□ are condensed and polymerized to produce an aliphatic polyamide polymer having repeating units, and Blocks in the block copolymer molecular chain (
The ratio of the total number of repeating units of A) to the total number of repeating units of block (B) is (A) / (B) = 9515 ~
Regarding the polyester porian mid strotta copolymerization method, which is characterized by the range of 5/95.

Polyester units The blocks constituting the aromatic polyester block (
Compounds used as A) include, for example, difunctional aromatic carboxylic acids represented by the general formula (where the needle in the formula represents a residue obtained by removing the carboxylic acid from a difunctional aromatic carboxylic acid) or an acid halide of the carboxylic acid and a difunctional phenol represented by the general formula 0 formula%) (wherein Ar' represents the residue of a difunctional phenol excluding the hydroxyl group). It is constructed by condensation polymerization.

As the difunctional aromatic carboxylic acid, those having the following structures are used, for example.

Two or more of these difunctional carboxylic acids or acid halides of the carboxylic acids may be used in combination.

Among these difunctional aromatic carboxylic acids, preferred are the difunctional aromatic carboxylic acids.

Further, as the difunctional phenol, for example, the following are used. General Formula % Formula % The most preferred difunctional phenol is bisphenol.

Polyamide units Examples of compounds used as the block (B) constituting the polyamide block include difunctional carbon atoms represented by the general formula % (wherein R1 is an alkylene group of 01 to CI2). It is formed by condensation polymerization of an acid or an acid halide of the carboxylic acid and a difunctional amine represented by the general formula % (wherein R2 is an alkylene group of C3 to C1□). be.

As the difunctional carboxylic acid, for example, one having a structure represented by the following formula -C is used. - Ship type Two or more of these difunctional carboxylic acids can be used in combination.

Among these compounds, preferred bifunctional carboxylic acids include aliphatic dicarboxylic acids represented by the general formula and acid halides of these aliphatic dicarboxylic acids.

The difunctional amine used has a structure represented by the following general formula. General formula % Formula %) These bifunctional amines can also be used in combination of two or more types.

Among these diamines, preferred difunctional amines are aliphatic diamines having the general formula % formula %: 48).

According to the present invention, the ratio of the total number of repeating units of block (A) to the total number of repeating units of block (B) in the copolymer molecular chain is (A) / (B) = 9515 to 5/95,
Preferably 90/10 to 10/90. More preferably, the thermal stability and heat resistance are in the range of 80/20 to 20/80.
A polyester polyamide copolymer with excellent processability is obtained.

The polyester polyamide copolymer of the present invention can be produced by a solution polymerization method, a melt polymerization method, or an interfacial polymerization method, but it is preferable to use a two-step interfacial polymerization method.

That is, the alkaline aqueous solution in which the difunctional phenol was dissolved in the first step and the Ninomiya functional acid halide dissolved in an organic solvent that is incompatible with water are mixed and reacted in the presence of a phase transfer catalyst. This produces the polyester of block (A).

Phenols? For example, caustic soda or caustic potash is used as the alkali for the decomposition, and the amount of the alkali is approximately equivalent to or more than the phenol. The concentration of phenols in the alkaline aqueous solution is in the range of 0.5 to 10% by weight, preferably 1 to 5% by weight. Examples of organic solvents that are incompatible with water include chlorinated hydrocarbons such as methylene chloride, chloroform, dichloroethane, trichloroethane, tetrachloroethane, and 1,2-dichloroethylene. The concentration of acid halides in the organic solvent is 0.5 to 10% by weight, preferably 1 to 5% by weight.
is within the range of

The polymerization reaction is preferably carried out at 40°C or lower. Polymerization time may generally be 20 minutes to 1 hour. As a phase transfer catalyst, trimethylhensylammonium hydroxide, trimethylhenselammonium chloride, triethylbenzylammonium chloride, tetrabutylammonium bromide, trioctylmethylammonium chloride, triphenylphosphonium iodide, triphenylmethylarsonium iodide, trimethyl Quaternary compounds such as octylarsonium iodide, 2-hydroxyphenyldimethylsulfonium chloride
Class ammonium salts, quaternary phosphonium salts, quaternary arsonium salts and tertiary sulfonium salts are used.

In the second step, block (B) is added to the aforementioned polyester solution.
A polyester polyamide copolymer is obtained by mixing and reacting an alkaline aqueous solution of the monomer, a difunctional amine, and a difunctional acid halide dissolved in an organic solvent that is incompatible with water. As the alkali, for example, caustic soda or caustic potash is used, and the amount of the alkali is approximately equivalent to or more than the amine. The concentration of amine in the alkaline aqueous solution is 0.5 to 15% by weight, preferably 2 to 15% by weight.
It is in the range of 10% by weight.

Examples of solvents that are incompatible with water include chlorinated hydrocarbons used in the production of component (A). The concentration of acid halides in the organic solvent is 0.5 to 15% by weight.
, preferably in the range of 2 to 10% by weight. The polymerization reaction is preferably carried out at 40°C or lower. Polymerization time is usually 10~
30 minutes is enough. In the condensation polymerization reaction by interfacial polymerization, it is necessary to disperse the organic solvent phase and the aqueous phase as uniformly as possible, and it is preferable to use a strong stirring device such as a homomixer or a line mixer.

To further specifically illustrate the production of polyester polyamide in the present invention, in the first step, a polycondensation reaction is carried out using equimolar amounts of bifunctional phenols and bifunctional acid halides or using an excess of either monomer.

Next, in the second step, the amine constituting component (B) is added in an amount such that the molar ratio of the total number of functional groups between the difunctional amine and the difunctional acid halide is in the range of i:o, s ~ 1.2. After adding the acid halide, a condensation polymerization reaction is performed to obtain the desired polymer. In order to obtain a high polymer by interfacial polymerization (A),
(B) The ratio of the number of reactive end groups between the difunctional phenol and difunctional amine of both components and the acid halide should be at least in the range of 1:0.8 to 1.2 in terms of molar ratio. It is.

The polyester polyamide profta copolymer produced according to the present invention has excellent thermal stability, heat resistance, and processability, as well as good transparency and mechanical strength, so it can be used for various purposes and can be used in ordinary molding. By using this method, it is possible to produce molded products, tapes, films, fibers, etc. for automobiles and electrical appliances.

When using the copolymer of the present invention, commonly added antioxidants, ultraviolet absorbers, lubricants, flame retardants, antistatic agents, colorants, fillers, glass fibers, and the like can be added. Furthermore, depending on the required performance, other known polymers such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, ABS HA resin, polyphenylene oxide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyacetal, polyamide, epoxy resin, polyfluoride etc. vinylidene dichloride, polysulfone, heptacryl polymer, ethylene-vinyl acetate copolymer, polybutadiene, styrene-butadiene copolymer, polyisoprene, natural rubber, butadiene-acrylonitrile copolymer, styrene-maleic anhydride copolymer,
Chlorinated butyl rubber, chlorinated polyethylene, ethylene-propylene copolymer, polyphenylene sulfide (PI
'S), polyetheretherketone, high impact polystyrene (HIPS) resin and the like.

e. Examples Hereinafter, the present invention will be explained in more detail with reference to Examples, but these are merely illustrative and do not limit the content of the present invention.

Example 1 First step After the glass reaction vessel equipped with a stirrer was sufficiently replaced with nitrogen,
0.650 g of caustic soda in 56 g of water in a nitrogen stream;
After dissolving a molar concentration aqueous solution of trimethylbenzylammonium chloride o, osoo of 0.911111, 1.70 g of bisphenol A is added and reacted while adjusting the liquid temperature to 5°C.

while 1.2 g terephthalic acid dichloride, 0.555
While adjusting g of isophthalic acid dichloride to 5°C,
Dissolve in 50 g of dichloromethane.

Next, while vigorously stirring the aqueous alkaline solution of bisphenol A and maintaining the reaction solution at 5° C., a dichloromethane solution of the acid dichloride is quickly added. Then, stirring was continued for 30 minutes while maintaining the temperature at 5°C, and the reaction of the first step was completed.

Second Step Next, 1.37 g of adipic acid dichloride is dissolved in 25 g of dichloromethane, and this is immediately added to the vigorously stirred first step polymer solution. After 1 minute, 0.780 g of caustic soda and an aqueous solution of 1.06 g of hexamethylene diamine dissolved in 27 g of water were quickly added to this solution with vigorous stirring, and the mixture was stirred vigorously at 5°C for 25 minutes. The reaction of the second step is completed.

- Separate the organic phase by allowing the obtained copolymer solution to stand still, add dilute hydrochloric acid, and wash thoroughly with water. The purified copolymer solution is poured into methanol to obtain a polymer precipitate. After thoroughly washing the obtained polymer with methanol, it is recovered and thoroughly dried in a vacuum dryer.

- Yarikinba Gitan The yield of the copolymer after drying was 3.38g, and the logarithmic viscosity was 0.
．． 83 (concentration in phenol/tetrachloroethane-1/l mixed solvent, 1.OOg/d i , 30°C), glass transition temperature, and melting temperature were measured using a differential thermal calorimeter (DSC).
) and were 189°C and 221°C, respectively. Vicat softening temperature (ASTM mouth 1525) is 190
℃, melt flow rate) (IR) (280℃, load 10kg, JIS 7210) is 29.1g/10
It was a minute. Furthermore, the results of infrared absorption spectrum (IR) analysis of the obtained copolymer are shown in FIG. Furthermore, 2
This copolymer press-molded into a sheet at 70°C was transparent and tough.

The evaluation results are shown in Table-1.

Example-2 In the first step, 2.10 g of bisphenol A, 0.7
74 g caustic soda, 1.12+++4+ trimethylbenzylammonium chloride o, osoo molar aqueous solution, 69 g water, 1.60 g terephthalic acid dichloride, 0.685 g isophthalic acid dichloride,
62 g dichloromethane, in the second step, 0.628 g hexamethylene diamine, 0.490 g caustic soda, 1
6g water, 0.614g adipic dichloride, l
Polymerization was carried out using 1 g of dichloromethane under the same conditions as in Example-1.

The yield of the obtained copolymer was 3.19 g. The physical properties were measured under the same conditions as in Example-1 and were as follows. Logarithmic viscosity 0.91, glass transition temperature 194°C, melting temperature 219°C, Vicat softening temperature 193°C, MFR
lo, 2g/10min.

The evaluation results are shown in Table-1.

Example-3 In the first step, 0.767 g of bisphenol A, 0.
305 g caustic soda, 0.41 ml trimethylbenzylammonium chloride 0.0500 molar aqueous solution, 25 g water, 0.763 g terephthalic dichloride, 0.327 g isophthalic dichloride, 3
0 g dichloromethane, in the second step, 1.30 g hexamethylene diamine, 1, 02 g caustic soda, 33
g water, 1.68 g adipic dichloride, 31 g
Polymerization was carried out under the same conditions as in Example-1, except that dichloromethane was used.

The yield of the obtained copolymer was 2.42 g. The physical properties were measured under the same conditions as in Example-1 and were as follows. Logarithmic viscosity 1. Ol, glass transition temperature 179°C, melting temperature 238°C, Bikanoto softening temperature 212°C, liver R11
3g/10 minutes.

The evaluation results are shown in Table-1.

Example-4 In the first step, 1.70g of bisphenol A, 0.65
0g of caustic soda, 0.91mj! Trimethylbenzylammonium chloride 0.0500 molar concentration water? 8
liquid, 56 g water, 1.29 g terephthalic acid dichloride, 0.555 g isophthalic acid dichloride, 50 g
Same as Example-1 except that in the second step, 1.06 g of hexamethylene diamine, 0.780 g of caustic soda, 27 g of water, 1.70 g of sebacyl dichloride, and 33 g of dichloromethane were used. Polymerization was carried out under the following conditions.

The yield of the obtained copolymer was 4.05 g. The physical properties were measured under the same conditions as in Example-1 and were as follows.

Logarithmic viscosity 1.08, glass transition temperature 185°C, melting temperature 192°C, Vicat softening temperature 186°C, liver R73.2
g/IO min. The evaluation results are shown in Table-1.

Example-5 1.70g of bisphenol A, 0.650 in the first step
g of caustic soda, 0.91 ml of trimethylbenzylammonium chloride, 0.0500 mol of agricultural water), 56 g of water, 1.29 g of terephthalic acid dichloride, 0.555 g of isophthalic acid dichloride, 50 g of dichloromethane, 2. Polymerization was carried out under the same conditions as in Example 1, except that 0.804 g of tetramethylene diamine, 0.780 g of caustic soda, 20 g of water, 1,79 g of sebacic acid dichloride, and 33 g of dichloromethane were used in the step. .

The yield of the obtained copolymer was 3.75 g. The physical properties were measured under the same conditions as in Example-1 and were as follows.

Logarithmic viscosity 1.13, glass transition temperature 188℃, melting temperature 218℃, Vicat softening temperature 190℃, liver R 36.5g
/10 minutes. The evaluation results are shown in Table-1.

Example-6 1.70g of bisphenol A, 0.650 in the first step
g of caustic soda, 0.91 ml of trimethylhensyl ammonium chlorite o, soo molar aqueous solution, 56
g of water, 1.29 g of terephthalic acid dichloride, 0.
555 g of isophthalic acid dichloride, 50 g of dichloromethane, in the second step, 0.804 g of tetramethylene diamine, 0.780 g of caustic soda, 27 g of water, 1
．． Polymerization was carried out under the same conditions as in Example-1 except that 37 g of adipic acid dichloride and 25 g of dichloromethane were used.

The yield of the obtained copolymer was 3.35 g. The physical properties were measured under the same conditions as in Example and were as follows.

Logarithmic viscosity 0.96, glass transition temperature 191°C, melting temperature 271°C, Vikaft softening temperature 194°C, liver R21.4g
/10 minutes. The evaluation results are shown in Table-1.

Comparative example-1 Polyester was produced only in the first step of Example-1.

The obtained polyester was not a high molecular weight polymer. The evaluation results of the polymer are shown in Table-1.

Comparative example-2 Polyamide was produced only in the second step of Example-1.

The yield of the obtained polymer is low. The evaluation results are shown in Table-1.

Comparative Example-3 The polyester of Comparative Example-1 and the polyamide of Comparative Example-2 were blended in the same composition ratio as Example-1 using a Henschel mixer and evaluated.

The physical properties of the blend were evaluated. Table 1 shows the evaluation results.
Shown below. Transparency and degree of Vikasoto softening are inferior to those of Example-1.

Comparative Example-4 Fully aromatic polyester U-100 (glass transition temperature 193°C) manufactured by Unitika G Kiku and nylon 66 CM manufactured by Toshi@
An equivalent mixture of pellets of 3006 (melting temperature 247°C) was pelletized in an extruder at 280'C and press-molded and was extremely opaque and brittle.

Comparative Example-5 Polyester was produced by the same method as the first step of Example-1, and in the second step, unlike the second step of Example-1, 0.135 g of caustic soda and 0.191 g of caustic soda were added to this polyester solution. A polyesteramide copolymer is produced by rapidly adding an aqueous solution of hexamethylene diamine dissolved in 20 g of water with vigorous stirring and vigorously stirring at 5° C. for 25 minutes. The copolymer was purified in the same manner as in Example-1.

The yield of the obtained copolymer was 2.61 g. The physical properties were measured under the same conditions as in Example-1 and were as follows. The processability was poor with a logarithmic viscosity of 0.98, a glass transition temperature of 196°C, a Vikaft softening temperature of 192°C, and an MFR of 4.6 g/10 minutes, and the obtained sheet was also translucent.

The evaluation results are shown in Table-1.

Effects of the Invention The polyester polyamide copolymer obtained by the present invention has excellent thermal stability, heat resistance, and processability, and therefore has great practical value as a molding material.

[Brief explanation of the drawing]

FIG. 1 is an infrared absorption spectrum diagram of the polyester polyamide bronok copolymer obtained in Example-1 of the present invention. Patent applicant: Japan Synthetic Rubber Co., Ltd. (2 idiots)

Claims (1)

[Scope of Claims] (A) A bifunctional aromatic carboxylic acid represented by the general formula ▲ Numerical formula, chemical formula, table, etc. available ▼ or an acid halide of the carboxylic acid, and a general formula HO-Ar'-OH. By condensation polymerization with the difunctional phenol shown, the general formula - [▲ Numerical formula, chemical formula, table, etc. are available▼] - [In the formula, Ar is a residue obtained by removing the carboxylic acid group from a difunctional aromatic carboxylic acid. , Ar' is a residue of a difunctional phenol from which the hydroxyl group has been removed. ] An aromatic polyester block having a repeating unit represented by the following is produced, and (B) a difunctional carboxylic acid represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc. ▼ or an acid halide of the carboxylic acid, and a general formula H_2N-R^2-NH_2 is condensed and polymerized with a difunctional amine represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ In the formula, R^1 and R^2 are C_1 to C_1_2 alkylene groups. be. ] is produced, and the total number of repeating units of block (A) in the entire block copolymer molecular chain and the block (
The ratio of B) to the total number of repeating units is (A)/(B) = 95
A method for producing a polyester polyamide block copolymer, characterized in that the polyester polyamide block copolymer has a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer having a polyester polyamide block copolymer.