JPS62181316A - Polyether ester amide resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled flexible composition having excellent breaking strength and high melt viscosity and suitable for blow-molding, by compounding a diisocyanate to a polyether ester amide consisting of an aminocarboxylic acid and a dicarboxylic acid, etc. CONSTITUTION:A polyether ester amide is produced by melt-polymerization of (A) a >=6C aminocarboxylic acid (e.g. omega-aminocaproic acid), lactam or a salt of a >=6C diamine and a dicarboxylic acid (e.g. salt of hexamethylenediamine and adipic acid), (B) a poly(alkylene oxide) glycol having a number-average molecular weight of 300-6,000 and (C) a 6-20C dicarboxylic acid (e.g. terephthalic acid). The copolymerized amount of the components B+C is e.g. 5-90wt%. The objective composition can be produced by melting and kneading a mixture obtained by mixing 100pts.wt. of the polyether ester amide with (D) 0.01-5pts.wt. of a diisocyanate (e.g. tolylene diisocyanate).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyetheresteramide resin composition that is flexible, has high breaking strength, and has high melt viscosity.

<Prior Art> Polyetheresteramides having polyamide repeating units, polyether repeating units, and ester bonds in the polymer main chain are known (US Pat. No. 3,044,987).
No. Specification).

<Problems to be solved by the invention> Polyether ester amide has excellent flexibility, lightness, transparency, and low-temperature impact resistance, and is less likely to cause cracks or sink marks during molding, so it is promising for injection molding applications. However, there are drawbacks such as easy discoloration, elastic recovery properties, and breaking strength, and improvements are desired. For example, high viscosity is necessary to manufacture tubes, bellows, etc. by extrusion molding or blow molding, but if the polymerization time is extended to obtain high viscosity, coloration tends to become severe. Furthermore, polyether ester amide has a relatively low melting point, making it difficult to perform in-phase polymerization, which necessitates liquid phase polymerization, which has the problem of increasing coloration.

The present invention has been made to solve the above-mentioned problems and to provide a polyether ester amide resin composition that is flexible, has high breaking strength, and has high melt viscosity.

As a result, the above-mentioned object of the present invention is to provide an aminocarboxylic acid or a lactam having 6 or more carbon atoms, or a lactam having 6 or more carbon atoms.
Salt (a) of the above diamine and dicarboxylic acid, poly(alkylene oxide) having a number average molecular weight of 600 to 6.000
0.01 parts by weight of diisocyanate (B) is added to 100 parts by weight of polyether ester amide compound consisting of glycol (b) and dicarboxylic acid (c) having 4 to 20 carbon atoms.
It has been found that this can be achieved by creating a resin composition characterized by containing ~5.0 parts by weight. The configuration of the present invention will be explained in detail below.

In the polyether ester amide (A) of the present invention, salts of aminocarboxylic acids or lactams having 6 or more carbon atoms or diamines and dicarboxylic acids having 6 or more carbon atoms (al is ω-aminocaproic acid, ω-aminoethenoic acid, ω -aminocaprylic acid, ω-aminopelargonic acid, ω
-aminocapric acid, 11-aminoundecanoic acid, 12
- Aminocarboxylic acids such as aminododecanoic acid or lactams such as cabrolactum, enanthracum, capryllactam, and laurolactam; There are salts of amine-dicarboxylic acids such as methylenediamine-adipate and 4,4'-diaminodicyclohexylmethane-dodecanedioate, but 11-aminoundecanoic acid and 12-aminododecanoic acid are particularly preferred. These can also be used in combination depending on the application.

It is also permissible to use other amide-forming components as copolymerization components in small amounts for the purpose of lowering the melting point of polyether ester amide or increasing adhesiveness.

The number average molecular weight of the polyether ester amide (A) of the present invention is 300 to 6. OOO poly(alkylene oxide) glycol (b) includes poly(ethylene oxide) glycol, poly(1,2- and 1,3-
Propylene oxide) glycol, poly(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, etc., among others. Poly(tetramethylene oxide) glycol is preferably used because of the excellent physical properties of polyether ester amide, such as heat resistance, water resistance, mechanical strength, and elastic recovery.

In particular, when further hydrophilicity is required for the effects of the present invention, poly(ethylene oxide) glycol is preferably used.

The number average molecular weight of poly(alkylene oxide) glycol can be used in the range of 600 to 6,000, but a molecular weight range that does not cause coarse phase separation during polymerization and has excellent low temperature properties and mechanical properties is selected, and this optimum molecular weight range is selected. The molecular weight region is poly(
(alkylene oxide) varies depending on the type of glycol.

For example, in the case of poly(ethylene oxide) glycol, 30
0-6. OD Ol Particularly preferably 400 to 4.00
3 if 0 is poly(propylene oxide) glycol
00 to 5,000, particularly preferably 500 to 0,000
However, in the case of poly(tetramethylene oxide) glycol, it is 500 to 3.000, particularly preferably 500 to 2.00.
A molecular weight range of 500 is used.

The dicarboxylic acids having 4 to 20 carbon atoms in the polyether ester amide prison of the present invention include terephthalic acid,
Isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4
1-dicarboxylic acid, diphenoxyethanedicarboxylic acid,
Aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate, 1,4-chlorohexanerecarboxylic acid, 1,
2-chlorohexanedicarboxylic acid, dicyclohexyl-
4,4'-; alicyclic dicarboxylic acid such as carboxylic acid,
and succinic acid, oxalic acid, adipic acid, sebacic acid,
Mention may be made of aliphatic dicarboxylic acids such as dodecanoic acid (decalcarboxylic acid) and ester-forming derivatives of these dicarboxylic acids.

In particular, dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, arepic acid, sebacic acid, and dodecanedioic acid and their ester-forming derivatives are preferred from the viewpoint of polymerizability, color tone, and physical properties of the polymer. used.

The dicarboxylic acid and its ester-forming derivative are
Depending on the purpose and use, one type or a combination of two or more types may be used.

In order for the effects of the present invention to be particularly noticeable in the middle stage, the amount of copolymerization of polyether ester units derived from poly(alkylene oxide) glycol (bl and dicarboxylic acid (e)) in polyether ester amide (containing polyether ester amide) is required. As 5～
90% by weight is preferred. When the amount of copolymerization is less than 5% by weight, flexibility and elastic recovery properties are lost, and when it exceeds 90% by weight, high temperature properties and mechanical properties are insufficient.

The method for polymerizing the polyether ester amide (including polyether ester amide) is not particularly limited, and any known method can be used. for example,
A polyamide prepolymer with carboxylic acid groups at both ends is produced by reacting aminocarboxylic acid or lactam, or a dicarboxylic acid salt ta+ with a raremine having 6 or more carbon atoms, and a dicarboxylic acid ((+). Carvone can be produced by reacting glycol (1)) under vacuum, or by charging the compounds of ta+, (1)), and (c) above into a reaction tank and reacting them by heating at high temperature in the presence or absence of water. A known method is to produce an acid-terminated polyamide prepolymer and then proceed with polymerization under normal pressure or reduced pressure. In addition, the above (n), (b), (c
There is also a method in which the compounds () are simultaneously charged into a reaction tank and melt-polymerized, and then the polymerization is proceeded all at once under high vacuum, but this method is preferable because it causes less coloring of the polymer.

In particular, when using sodium 3-sulfoinophthalate or its ester-forming derivative, it is reacted with poly(alkylene oxide) glycol in one reaction tank, and other raw materials are reacted in another reaction tank. A method in which both are then melt-mixed and polymerized under high vacuum is preferred.

The diisocyanate (B) in the present invention includes 4.
4-diphenylmethane diisocyanate (MDI),
Tolylene diisocyanate (TDI), xylene diisocyanate (XDI), 1,5-naphthylene diisocyanate (MDI), hexamethylene diisocyanate (
HMDI), hydrogenated MDI, hydrogenated TD■, isophorone diisocyanate (IPDI), lysine diisocyanate (
LDI), isopropylidene bis(4-cyclohexyl isocyanate) (IPCI), among others, M
DI, TDI, and HMDI are preferably used.

In the present invention, the blending ratio of polyether ester amide powder and diisocyanate (Bl) is 0.01 to 5.0 parts by weight, preferably 0.01 to 5.0 parts by weight, per 100 parts by weight of the powder.
It is necessary to adjust the proportion to be 0.05 to 2.0 parts by weight, particularly preferably 0.1 to 1.0 parts by weight. (B) is 0.
If the amount is less than 1 part by weight, the effect of improving the breaking strength and high viscosity of the present invention will be small, and if it exceeds 5.0 parts by weight, the thermoplasticity of the polyether ester amide will be impaired, which is not preferable.

The resin composition of the present invention is preferably melt-kneaded, and known methods can be used for melt-kneading. For example, the resin composition can be prepared by melt-kneading the resin composition using a Banbury mixer, a rubber roll machine, a screw-screw or twin-screw extruder, etc., usually at a temperature of 100 to 300°C. Diisocyanate can also be added at the end of polymerization of the polymer.

During melt-kneading, the terminal groups of the polyether ester amide prisoner react with the diisocyanate (I3) to increase the molecular weight.

Therefore, the breaking strength increases and the melt viscosity increases.

The resin composition of the present invention also contains known antioxidants, thermal decomposition inhibitors, ultraviolet absorbers, hydrolysis resistance improvers, colorants (
pigments, dyes), antistatic agents, conductive agents, flame retardants, reinforcing agents,
Fillers, lubricants, nucleating agents, mold release agents, plasticizers, adhesion aids, adhesives, and the like can be optionally contained.

The present invention will be explained below with reference to Examples.

<Examples> Unless otherwise specified in the examples, parts mean parts by weight.

Reference Example Production of Polymer A Polymerization of Polymer (A-1) 81.9 parts of ω-aminododecanoic acid, 6.8 parts of dodecanedioic acid
part, and 19.3 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 650.
1098 (antioxidant) into a reaction vessel equipped with a helical ribbon stirring blade, purged with nitrogen, heated and stirred at 260°C for 1 hour to obtain a homogeneous transparent solution,
Antimony trioxide catalyst 0.015 parts, monobutyl monohydroxytin oxide catalyst 0.015 parts, phosphoric acid 0.015 parts.
[105 parts (anti-coloring agent) were added and the polymerization conditions were brought to below 1 mmflB in 1 hour according to the vacuum program. When reacted under these conditions for 2.5 hours, a viscous, colorless and transparent molten polymer was obtained, and when this polymer was discharged into water as a gut, it crystallized and turned white. The obtained polyether ester amide (A-1) has a relative viscosity (ηr) of 1.81 measured in orthochlorophenol at 25°C at a concentration of 0.5%, and a crystal melting point by DSC of 1.
The temperature was 67°C.

Polymerization of polymer (A-2) 49.1 parts of ω-aminododecanoic acid, 7.9 parts of terephthalic acid
48.8 parts of poly(tetramethylene oxide) glycol with a number average molecular weight of 1020, 11 Irganox"
1098 0.5 part, antimony dioxide 0.015 part,
Polyether ester amide (A- 2) was obtained.

Polymerization of polymer (A-3) 27.6 parts of ω-aminododecanoic acid, 5.7 parts of terephthalic acid
parts, 70.5 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 2060, 0.5 parts of II Irgano, Cus 1098, 0.015 parts of antimony trioxide, 0.015 parts of monobutyl monohydroxytin oxide,
and 0.005 part of phosphoric acid under the same conditions as Polymer (A-1) to obtain polyetheresteramide (A-3) having a relative viscosity of 1.92 and a melting point of 145°C.

The abbreviations and compositions of the diisocyanates used in the diisocyanate examples and comparative examples are as follows.

Examples 1 to 7, Comparative Examples 4 to 6 (Comparative Examples 1 to 3 will be described later) Triblend of polyether ester 7mid (A-1), (A-2), and (A-3) with the diisocyanates shown in the table. The mixture was melt-kneaded in a 50 m1φ extruder heated to 200°C, and then pelletized. 5 of the obtained berets
200℃ using an injection molding machine with an injection capacity of oz.
Also, a JI No. 82 tensile test piece was molded at a mold temperature of 40°C. Hardness meets ASTM D-2240, tensile properties meet ASTM D-658, and melt index meets ASTM
Measured according to D-1233.

The results are shown in the table.

Comparative Examples 1 to 3 Hardness, tensile properties, and melting index of polyether ester amides (A-1), (A-2), and (A-3) were measured in the same manner as Examples 1 to 7 and Comparative Examples 4 to 6. did.

The results are shown in the table.

The following can be seen from the results in Table 1.

Comparing Examples 1 to 7 with Comparative Examples 1 to 3, it can be seen that the resin compositions of the present invention have large breaking stress and high melt viscosity while maintaining the flexibility of polyether ester amide.

As seen in Comparative Examples 4 to 6 (this diisocyanate was
．． If the amount exceeds 0 parts by weight, the viscosity will increase significantly and thermoplasticity will be lost.

Example 8 26°2 parts of hexamethylenediamine-adibate and 8.2 parts of adipic acid were added to Irganox 11109B.
(Antioxidant) 0.25 part and antimony dioxide catalyst 0.05 part were charged into a reaction vessel equipped with a helical ribbon stirring blade, and the mixture was purged with nitrogen and heated and stirred at 220° C. for 1 hour (reactant (a)).

On the other hand, poly(ethylene oxide) with a number average molecular weight of 600
62.6 parts of glycol and 14.2 parts of 6-nadriium sulfoisofucric acid dimethyl ester were mixed with 0.25 parts of I+Irganox 1010 (antioxidant) and 0.05 parts of tetrabutyl titanate catalyst using a helical ribbon stirring blade. The mixture was placed in another reaction vessel equipped with the same equipment and heated and stirred at 240°C for 1 hour (reactant (b)). Reactant (b) was added to reactant (a), and the mixture was heated and stirred at 225°C for 60 minutes under a nitrogen stream. After that, a transparent homogeneous solution was obtained, and the polymerization conditions were brought to 240°C and 0.5M1 (below III) according to the temperature increase and pressure reduction program. When the polymerization reaction was carried out under these conditions for 5 hours and 30 minutes, a viscous, colorless and transparent solution was obtained. A molten polymer was obtained. After lowering the temperature of the reaction vessel to 200°C, a portion of the polymer was discharged onto a cooling belt in a glob shape and pelletized to obtain polyether with a relative viscosity of 1.80 and a melting point of 165°C. Esteramide (A-4) was obtained.Next, 0.35 parts of hexamethylene diisocyanate was added to 70 parts of the polymer remaining in the reaction vessel, and 1
After stirring for 0 minutes, the mixture was discharged onto a cooling belt to form pellets.

11 by hot pressing pellets heated to 180℃
A sheet with a thickness of 1N was prepared, and its physical properties were measured.

Hydrophilicity was determined by observing the state when the sheet was immersed in water at 23° C. for 1 day, and tensile properties were determined according to JIS K6301. Hardness was determined according to ASTM D-2240, and was measured by stacking four notebooks.

Melt index is according to ASTM D-1233.

The results are shown in Table 2.

Ratio 1 Example 7 The physical properties of polyether ester amide (A-4) were measured in the same manner as in Example 8.

The results are shown in Table 2.

Table 2 In Table 2, when compared with Example 8 and Comparative Example 7, the resin composition of the present invention had a large breaking stress and a high melt viscosity while maintaining the hydrophilicity and flexibility of polyether ester amide. ing.

<Effects of the Invention> According to the present invention, by blending a specific amount of diisocyanate into polyether ester amide, the breaking strength of the polyether ester amide can be increased while maintaining its flexibility.

Also, melt viscosity increases by melt-kneading, so
It has the effect of increasing the melt viscosity of polyether ester amide, which has a short liquid phase polymerization time and little coloring, to a level suitable for blow molding without solid phase polymerization.

Claims (1)

[Claims] Aminocarboxylic acids or lactams having 6 or more carbon atoms,
Or a salt of diamine and dicarboxylic acid having 6 or more carbon atoms (
a), poly(alkylene oxide) glycol (b) having a number average molecular weight of 300 to 6,000, and having 4 carbon atoms
A polyether ester amide resin composition characterized by blending 0.01 to 5.0 parts by weight of a diisocyanate (B) to 100 parts by weight of a polyether ester amide (A) composed of ~20 dicarboxylic acids (c). thing.