JPS6330927B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polyetherester block copolymer composition having excellent heat deterioration resistance and hydrolysis resistance. Polyether ester block copolymers having alternating polyether and polyester parts in their molecular chains are known as polymers with rubber-like elasticity and are useful as fibers, films, and molded products. However, since polyether ester block copolymers contain unstable polyether blocks in their main chains, they are susceptible to oxidative deterioration, and as the degree of polymerization decreases, mechanical properties decrease, surface cracks occur, coloring and severe When this happens, undesirable phenomena such as decomposition and volatilization of polyether occur. In particular, this oxidative deterioration is accelerated by heat, and its use is restricted in high-temperature atmospheres. In order to improve these properties, the addition of antioxidants such as hindered phenols, aromatic amines, sulfur compounds, and phosphorus compounds has been considered to prevent thermal deterioration. However, there is a problem with coloring of the polymer due to antioxidants, and the effect of improving heat resistance is insufficient. In addition, since polyether ester block copolymers have ester groups in their molecular chains, they are susceptible to hydrolysis, and when placed in water, alcohol, acidic or alkaline solutions, their physical properties decrease as the degree of polymerization decreases. Therefore, there are restrictions on its use in this respect as well. In order to improve these properties, a method has also been proposed in which a compound having a reactive polyfunctional group is added to the polyether ester block copolymer to block the terminal groups of the copolymer. For example, JP-A-49-
Publication No. 13298 describes a method for improving abrasion resistance, hydrolytic stability, and high-temperature properties by adding a difunctional or higher-functionality polyepoxide and a curing agent to a polyether ester block copolymer. Polyglycidyl ether compounds derived from epichlorohydrin and phenols or epichlorohydrin and alcohols are described in the Examples. It is true that abrasion resistance etc. can be improved by blocking the terminals of a polyether ester block copolymer with a polyglycidyl ether compound, but the polyglycidyl ether compound itself has poor reactivity, so it is difficult to use curing agents such as polyamines. I need. It was also found that sufficient improvement effects could not be obtained simply by blending the curing agent into the polyether ester block copolymer without using a curing agent. Therefore, the present inventors have developed a compound that is highly reactive to polyether ester block copolymers and that can reliably improve the heat deterioration resistance or hydrolysis resistance of polyether ester block copolymers simply by blending them. As a result of intensive studies, we have arrived at the following invention. That is, the present invention provides a polyether ester block copolymer composition characterized in that 0.01 to 20% by weight of a glycidyl ester compound represented by the following general formula is blended with the polyether ester block copolymer. It is something. (In the formula, R is an n-valent organic carboxylic acid residue having 1 to 30 carbon atoms, and n is an integer of 1 to 4.) The polyether ester block copolymer in the present invention refers to a polyester hard segment. It is a copolymer consisting of polyether soft segments with a number average molecular weight of approximately 200 to 6000, and the ratio of hard segments to soft segments is 15 to 90% by weight.
85 to 10% by weight. Dicarboxylic acid components forming polyester hard segments include terephthalic acid, isophthalic acid, phthalic acid,
Aromatic dicarboxylic acids such as 2,6- and 1,5-naphthalene dicarboxylic acid, bis(p-carboxyphenyl)methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid,
Examples include alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, cyclopentanedicarboxylic acid, and 4,4'-dicyclohexyldicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and dimic acid. but,
From the viewpoint of mechanical properties and heat resistance, it is preferable to use aromatic dicarboxylic acid in an amount of at least 50 mol %, and use of terephthalic acid is particularly recommended. In addition, the diol components constituting the hard segment include aliphatic or alicyclic diols having 2 to 12 carbon atoms, such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol,
1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, bis(p
Bisphenols such as -hydroxy)diphenyl, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)propane and mixtures thereof may be used, but especially aliphatic or alicyclic groups having 2 to 8 carbon atoms. Diols are preferably used. In addition, the poly(alkylene oxide) glycols constituting the polyether soft segment are polyethylene glycol, poly(1,3- and 1,
2-propylene glycol, poly(tetramethylene oxide) glycol, polyethylene glycol polypropylene glycol block copolymer,
These include polyethylene glycol-poly(tetramethylene oxide) glycol block copolymers, and poly(tetramethylene oxide) glycol is particularly preferred, although it is of course possible to use these in combination. The average molecular weight of these polyether glycols ranges from about 200 to 6000. The polyether ester block copolymer made of these components can be produced by any method, but one example of a suitable polymerization method is to add dimethyl ester of dicarboxylic acid to an excess of about 1.2 to 2.0 moles relative to the acid.
A heating reaction is carried out with twice the molar amount of low molecular weight glycol and poly(alkylene oxide) glycol at a temperature of about 150 to 260°C under normal pressure in the presence of a normal esterification catalyst to perform transesterification and distill off methanol. It can be produced by heating polycondensation at 200 to 270°C under reduced pressure of 5 mmHg or less. If necessary, a polyfunctional copolymer component that can be partially chemically crosslinked, such as polycarboxylic acid, polyol, polyoxycarboxylic acid, etc., may be used in the polyether ester block copolymer. The glycidyl ether compound blended into the polyether ester block copolymer in the composition of the present invention is represented by the following general formula. (In the formula, R is an n-valent organic carboxylic acid residue having 1 to 30 carbon atoms, and n is an integer of 1 to 4.) Here, R is an n-valent organic carboxylic acid residue having 1 to 30 carbon atoms. It is a residue, and includes aliphatic groups with 30 or less carbon atoms, alicyclic groups such as cyclohexylene, phenylene, naphthylene,

【formula】

【formula】

【formula】

【formula】

It contains an aromatic group such as [Formula]. n is 1~
It is an integer of 4. Here, specific examples of the glycidyl ester compounds include glycidyl benzoate, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, Behenic acid glycidyl ester, versatile acid glycidyl ester, oleic acid glycidyl ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester,
Behenolic acid glycidyl ester, stearic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, bibenzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclohexanedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid Examples include diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetraglycidyl ester, etc., and these may be used singly or in combination.
More than one species can be used. The amount of glycidyl ester compound added is 0.01 to the polyether ester block copolymer.
A range of ~20% by weight, preferably 0.05 to 10% by weight is appropriate, and if it is less than 0.01% by weight, a sufficient effect of improving heat deterioration resistance and hydrolysis resistance cannot be obtained.
Moreover, if the content is 20% by weight, gelation of the polymer tends to occur during compounding or molding, which is not preferable. The method for adding a glycidyl ester compound to a polyether ester block copolymer is as follows:
Examples include a method of melt-mixing immediately after polymerization, or a method of melt-mixing after polymerization (before molding).
The latter is particularly preferred. The heat deterioration resistance of the composition of the present invention is further improved by adding heat-resistant stability. Examples of these stabilizers include 4,4'-bis(2,6-di-tertiary
butylphenol), 1,3,5-trimethyl-
2,4,6-tris(3,5-di-tert-butyl-4
-hydroxybenzyl)benzene, tetrakis[methylene-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, hexamethylene glycol bis[β-(3,5-di-tert-butyl-4-) hydroxyphenyl)propionate], 6-(4-hydroxy-3,5-di-tertiary)
butylanilino)-2,4-bisoctylthio-
1,3,5-triazine, 2,2'-thiodiethyl-bis[3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3(3,5-di-tert-butyl- 4-hydroxyphenyl) propionate, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamide, tris(3,5-di-tert-butyl-4-hydroxyphenyl) enyl) isocyanurate, tris[β-(3,5-di-tert-butyl-
Various hindered phenols such as 4-hydroxyphenyl) propionyl-oxyethylene] isocyanurate, N,N'-bis(β-naphthyl)
-p-phenylenediamine and 4,4'-bis(4-
Aromatic amines such as α,α-dimethylbenzyl)diphenylamine, thioether compounds such as dilaurylthiodipropionate and distearylthiodipropionate, triphenylphosphite, trinonylphosphite, and tricresylphosphite. Examples include phosphite compounds, thiophosphite compounds such as trinonyltrithiophosphite, trilauryltrithiophosphite, and triphenyltrithiophosphite. In particular, when one or both of a thioether compound or a thiophosphite compound is added to hindered phenols, excellent heat deterioration resistance without coloring can be obtained. In addition, the polyether ester block copolymer composition of the present invention may contain light stabilizers such as substituted benzophenones, benzotriazoles, and piperidine compounds, colorants (application materials, dyes), antistatic agents, conductive agents, crystal nuclei, etc. Additives such as agents, lubricants, fillers, reinforcing agents, adhesion aids, plasticizers, mold release agents, and flame retardants may be optionally blended. The present invention will be explained below with reference to Examples. In the examples, all "parts" or "%" are expressed as weight ratios. Further, the logarithmic viscosity shown in the text and examples is a value measured in orthochlorophenol at 30°C and at a concentration of 0.5%. Example Polymer A 90.8 parts of dimethyl terephthalate, 30.3 parts of dimethyl isophthalate, 69.0 parts of poly(tetramethylene oxide) glycol having a number average molecular weight of 1000, and 84.2 parts of 1,4-butanediol were stirred in a helical ribbon type with 0.10 part of titanium tetrabutoxide catalyst. The mixture was charged into a reaction vessel equipped with blades and heated at 210°C for 2 hours to distill off 95% of the theoretical amount of methanol from the system. Next, the temperature was raised to 245°C, and the pressure inside the system was reduced to 0.2 mmHg over 50 minutes, and polymerization was carried out under these conditions for 2 hours. The resulting polyether ester (A) has a melting point of 162℃ and a logarithmic viscosity.
It was 0.98. Polymer B: 194 parts of dimethyl terephthalate, number average molecular weight
Polyether ester (B ) was obtained. Polymer C: 48.4 parts of dimethyl terephthalate, number average molecular weight
2000 poly(tetramethylene oxide) glycol 110 parts, ethylene glycol 44.0 parts, zinc acetate
From 0.080 parts and germanium dioxide 0.048 parts,
Polymerized under the same conditions as Polymer A, melting point 210℃,
A polyether ester (C) with a logarithmic viscosity of 1.3 was obtained. Examples 1 to 5 and Comparative Examples 1 to 5 1.0% or 2.0% of the glycidyl ether compounds listed in Table 1 or a comparative glycidyl ether compound or polycarbodiimide compound was blended with polyether ester (A), and the mixture was heated to 240°C. The mixture was melt-kneaded in a heated 30 mmφ extruder and then pelletized. After vacuum drying the pellets,
It was pressurized at 240°C to form a press sheet with a thickness of 0.9 to 1.1 mm and punched into JIS K-6301 No. 3 dumbbell-shaped test pieces. The test piece was aged in a hot air oven at 140°C to determine its heat resistance life. The heat-resistant life was defined as the time when the retention rate of elongation at break reached 50%. In addition, the test piece was placed in a stainless steel pressure cylinder with water at 100°C.
The hydrolysis life was determined by heating. The hydrolysis life is similar to the heat life, and the elongation retention rate at break is 50.
%.

[Table] As is clear from the examples and comparative examples, excellent heat deterioration resistance and hydrolysis resistance can be obtained only when a glycidyl ester compound is added, and excellent resistance to heat deterioration and hydrolysis can be obtained by adding a glycidyl ether compound or a polycarbodiimide compound. , only a slight improvement effect was observed. Examples 6 to 7, Comparative Examples 6 to 9 An injection molding machine in which the glycidyl ester compound and heat stabilizer listed in Table 2 were blended with polyether ester (B) or polyether ester (C) and heated to 240°C. A JIS K7113 No. 2 dumbbell-shaped test piece was molded from the sample. This test piece was aged in a hot air oven at 140°C, and the heat resistance life and presence or absence of yellowing were examined. In addition, as a comparison, a compound other than the glycidyl ester compound and a heat-resistant stabilizer were blended, and after molding into a test piece in the same manner as in the example, the heat deterioration resistance was examined.

【table】

[Table] As is clear from the Examples and Comparative Examples, when the glycidyl ester compound of the present invention and a heat-resistant stabilizer are added, a composition with good heat deterioration resistance without yellowing can be obtained. When only a heat stabilizer was added without adding an ester compound, or when a glycidyl ether compound or a polycarbodiimide compound and a heat stabilizer were added, yellowing occurred and the heat deterioration resistance was considerably inferior to that of the composition of the present invention. I can only get it.

Claims (1)

[Scope of Claims] 1. A polyether ester block copolymer composition comprising 0.01 to 20% by weight of a glycidyl ester compound represented by the following general formula based on the polyether ester block copolymer. (In the formula, R is an n-valent organic carboxylic acid residue having 1 to 30 carbon atoms, and n is an integer of 1 to 4.)