JPS59152951A - Polyester type block copolymer composition - Google Patents

Abstract

PURPOSE:The titled composition that is obtained by adding a combination of a specific epoxy compound with a heat stablizer, thus showing greatly improved heat resistance and water resistance. CONSTITUTION:A polyester type block copolymer which is obtained by reaction of a crystalline aromatic polyester with a lactone is combined with a one or more functional epoxy compound and a heat stablizer selected from hindered phenols, sulfur compounds and diphenylamines. As the crystalline aromatic polyester, is polyethylene terephthalate with a molecular weight of more than 5,000 and less than 1.5 equivalent/kg acid value. The lactone is preferably epsilon-caprolactone. The epoxy compound has 0.9-14 equivalents/kg epoxy value and is added by 0.2-10wt% based on the block copolymer, while the heat stablizer is a hindered phenol and the amount to be added is 0.05-5wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in heat resistance, water resistance, etc. of a polyester-type block copolymer having rubber-like elasticity obtained by reacting a crystalline aromatic polyester with a lactone. Yes The above polyester type block copolymer has excellent rubber-like elastic properties and excellent light resistance, but has the drawback that strength and elongation decrease when exposed to high temperatures for a long time. In addition, it is easily hydrolyzed by water, so it cannot be put to practical use as fibers, films, or various molding materials as it is.

In order to overcome these drawbacks, a method of adding polycarbodiimide, etc., which is a hydrolysis-resistant agent to polyester, has been known for a long time, but although this method improves the durability against hydrolysis, it However, it is expensive and has drawbacks such as discoloration of the polymer when heated for a long time. Additionally, in order to improve heat resistance, it is possible to incorporate hindered phenol-based or nitrogen-based stabilizers, but simply adding these heat stabilizers to the above polyester block copolymer is not practical. However, no effect on improving heat resistance was observed.

However, the present inventors have discovered that heat resistance can be significantly improved by blending a monofunctional or more functional epoxy compound and a heat stabilizer together, and have thus arrived at the present invention.

That is, the present invention provides a polyester type block copolymer obtained by blending a monofunctional or more functional epoxy compound and a heat stabilizer with a polyester type block copolymer obtained by completely reacting a crystalline aromatic polyester with a lactone. It is a combined composition.

When an epoxy compound is used in the above polyester type block in combination with a heat stabilizer as in the present invention, the heat resistance is significantly improved compared to when the epoxy compound is used alone.

The polyester type block copolymer in the present invention is obtained by reacting a crystalline aromatic polyester with a lactone. In the present invention, the crystalline aromatic polyester is
A polymer consisting mainly of ester bonds or ester bonds and ether bonds, having at least one type of aromatic group as the main repeating unit, and having a hydroxyl group at the end of the molecule. The crystalline aromatic polyester is preferably a polyester having a melting point of 150° C. or higher when a high degree of polymerization is formed. As a molding material, molecule -1j1
The molecular weight is preferably 5,000 or more, but in the case of adhesives and coatings, the molecular weight may be 5,000 or less. Moreover, those having an acid value of 1.5 equivalents or less than 1 mole are preferable.

Preferred specific examples include polyethylene terephthalate, polytetramethylene terephthalate, poly-1,4-
Homopolyesters such as cyclohexylene dimethylene terephthalate and polyethylene-2,6-su7talate,
Polyester ethers such as polyethylene oxybenzoate and poly-p-phenylene bisoxyethoxy terephthalate, ti mainly consist of tetramethylene terephthalate units or ethylene isophthalate units, and may also include tetramethylene isophthalate units, ethylene isophthalate units, and tetramethylene isophthalate units. Copolymerization of methylene adipate units, ethylene adipate units, tetramethylene sebacate units, ethylene sebacate units, 1,4-cyclohexylene dimethylene terephthalate units, tetramethylene-p-oxybenzoate units, ethylene-p-oxybenzoate units, etc. Examples include copolymerized polyester or copolymerized polyester ether having components. In the case of a copolymer, it is preferable that the copolymer contains 60 moles or more of tetramethylene' or ethylene terephthalate units.

On the other hand, as the lactone, ε-caprolactone is most preferred, but enantlactone, cabrylolactone, etc. can also be used. Furthermore, two or more of the above lactones can be used in combination.

The copolymerization ratio of the aromatic polyester and lactones is 97/3 to 5/95, especially 9515 to 30/7 in weight ratio.
0 is preferred. Furthermore, the above-mentioned crystalline aromatic polyester and lactones are reacted by adding a catalyst as necessary and heating and mixing them. The structure is not particularly limited as long as it has the following formulas (I) and (II), but it is not limited to these compounds. It's not something you can do.

(In the formula, R1 is a hydrocarbon group having 1 to 4 carbon atoms with or without a side chain, R is an alkylene group with or without a side chain,
ru is a divalent hydrocarbon group with or without a side chain, m is O
20) More specifically, the following compounds are exemplified. Methyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol monophenyl monocricidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, etc.

Note that the epoxy compound of the present invention has an epoxy value of 0.
9 to 14 lids/God is preferred. The amount of the epoxy compound used varies depending on the amount of terminal groups of the polyester type block copolymer required, but it is usually 0.2 to 10% by weight, and 0.5 to 4% by weight relative to the block copolymer. Weight clerk is preferred. If it is less than 0.2% by weight, the effect of heat resistance and water resistance will decrease -vlOf
If it exceeds fii%, the surface condition of the molded product tends to become rough due to the influence of unreacted epoxy compounds.

The epoxy compound and the polyester type block copolymer are usually mixed by melt mixing, and although no catalyst may be used, the reaction is significantly accelerated by using a catalyst or a curing agent. As the catalyst or curing agent, all those generally used in the reaction of epoxy compounds can be used, including amines, phosphorus compounds, monocarboxylic acids or dicarboxylic acids having 10 or more carbon atoms, Ia of the Periodic Table of Elements. Alternatively, compounds such as Group IIa metal salts are used alone or in combination of two or more. Among them, trivalent phosphorus compounds such as tributylphosphine and triphenylphosphine are preferred.

The melt-mixing temperature is preferably from 3°C higher than the crystalline melting point of the block copolymer to 280°C. The mixing time is approximately 30 seconds to 120 minutes and is appropriately selected depending on the mixing method and temperature.

Examples of the heat stabilizer used in the present invention include hindered phenol compounds, sulfur compounds, and those of the general diphenyl formula.

R4 K! Or, it is any hydrocarbon having 1 to 18 carbon atoms having one or more of 1 in the molecular chain or at the end of the molecule, or as a substituent, and R' is a hydrocarbon having 1 to 18 carbon atoms which may be substituted with a hydroxyl group.
represents a hydrocarbon group, R1 and R2 are hydrogen atoms and alkyl groups having 1 to 18 carbon atoms, which may be the same or different, t is O-2, m is 1-4, and n is It is an integer from 0 to 1 and is equal to the total valency of t-1-m id R. ) Examples of the compound represented by the above general formula (1) are:
Examples include: 3,5-ditertiary butyl-4-hydroxyhydrocinnamic acid octyl ester, 3-ditertiary butyl-4-hydroxyhydrocinnamic acid nonyl ester, ethylene glycol bis(3,5-ditertiary butyl-4- hydroxyhydrocinnamic acid) ester, glycerin tris(3,5-ditertiary butyl-4-hydroxyhydrocinnamic acid) ester, pentaerythritol tetrakis (3,5-ditertiary butyl-4-hydroxyhydrocinnamic acid) ester, Pentaerythritol tetrakis [3(3,5-di-tert-butyl-4-hydroxyphenyl)propione-)) 3-5-di-tert-butyl-4
-Hydroxycinnamic acid-4=tertiary butylph-9-enyl ester, N-[3-(3,5-ditertiary 7'thyl-4-hydroxyphenyl)flopionylcou-4-aminephenol, N-[3-( 4-hydroxyphenyl)acryloyl-4-aminephenol, N-stearoyl-6-di-tert-butyl-4-aminoneenol, N-(3-(3.5-di-tert-butyl-4-hydroxyphenyl)propionyl) -2,6-di-tertiary-butyl-4-aminephenol, N-stearoyl-4-hydroxy-3,5-di-tertiary-butylbenzylamine, N-stearoyl-4-hydroxy-3,5-di-tertiary Butylphenethylamine, N-(3-(4-hydroxy-3.
5-ditertiary-butylphenyl)propionyl]-4-
hydroxy-3,5-ditertiary butylbenzylamine,
N@N'-bis(4-hydroxy-3,5-di-tert-butylphenethyl)adipine iW7mide, 2,2'-thiobis(4-tert-butylphenol), 2,2'-thiobis(4-tert-butylphenol), 6-di-tert-butylphenol), 4,4'
-thiobis(2-6-di-tert-butylphenol), distearyl-3,5-10-di-tert-butyl-4-hydroxybenzylphosphonate, diphenyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate , distearyl-3,5-di-tert-butyl-4-hydroxyphenylphosphonate, stearyl-bis(3,5-citris(3-di-tert-butyl-4-hydroxyphenyl) phosphate).

Further, examples of the compound represented by the above general formula (2) include the following. 2,6-1 di-tert-butyl-4-methylphenol, 2-6-1-di-tert-butyl-4-octylphenol, 2-methyl-6-tert-butyl-4-methylphenol and 2,2'-methylenebis(
4-tythyru-6-tertiary 7' thylphenol), 2.
2'-methylenebis(4,6-di-tertiary butylphenol), 4-4'-methylenebis(2,6-di-tertiary-butylphenol), 2,2'-ethylidenebis(4,6-di-tertiary-butylphenol) butylphenol), 4,4'-impropylidenebis(206-di-tert-butylphenol)41-1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 2,4 -6-tris(3
-5-ditertiary-butyl-4-hydroxybenzyl) mesitylene.

Examples of sulfur-based compounds include those having the following general formula.

(R,) (-8-Rt)p (3)(
In the formula, R1 is a hydrocarbon group having 1 to 18 carbon atoms, or -COO-1-OCO-1-cod-, -N
Indicates a hydrocarbon group having 2 to 23 carbon atoms having either an HCO- bond, R4 is a hydrogen atom or the same hydrocarbon group as R1, and the total number of carbon atoms in Rs and the number of carbon atoms in R4 is 7 or more. Specific examples of the compound represented by the above general formula (3) include the following: 0-di-n-hexyl sulfide, distearyl sulfide, dibenzyl sulfide, diphenyl sulfide, dioctylthiodipropionate, lauryl thiodipropionate, thiodiethanol dilaurate, bis(dodecylthio)methane,
1,1-bis(stearylthio)ethane, phenyl-bis(laurylthio)methane, dodecylmercaptan, thioglycolic acid lauryl ester, 3-mercaptopropionic acid stearyl ester, 3-mercaptofuropionic acid benzyl ester, 4-mercaptobutyric acid lauryl ester Ester, 6-mercaptocaproic acid stearyl ester, mercaptopropionic acid ethylene glycol ester, thioglycolic acid pentuquinone ester, glycerin tris(6-mercaptocaproic acid) ester, N-stearyl-mercaptoglycolic acid amide, thioglycolic acid anilide, 3 -Mercaptopropionic acid anilide, 4-mercaptobutyric acid anilide, N-lauryl-4-mercaptobutyric acid amide, 6-mercaptocaproic acid anilide, N-N'-bis(3-mercaptopropionyl)xylylenediamine ○In addition, the above diphenylamine compounds Examples include the following general formula.

(In the formula, R5, R1, R7, and R8 represent a hydrogen atom or a hydrocarbon group having 1 to 13-4 carbon atoms.) Examples of the compound of the above general formula (4) include 4,4'-bis( α,α-dimethylbenzyl)diphenylamine, 4
-4'-bis(α-methylbenzyl)diphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, 4-4'-bis(α-methylbenzyl)diphenylamine, 4,4'-bis( Examples include α-methyl-α-ethylbenzyl)diphenylamine, 4-(α-methylbenzyl)-4'-(α'-ethylbenzyl)diphenylamine, and 4,4'-pisbenzyldiphenylamine.

The amount of each heat stabilizer added is 0.05 to 5% by weight, preferably 0.05 to 5% by weight, based on the polyester block copolymer.
．． It is 1 to 1.0% by weight. However, if a large amount, for example 5% by weight or more, is used, there is a drawback that the heat stabilizer will precipitate. Note that among the above heat stabilizers, the hindered phenol heat stabilizer is the most effective. The mixing may be performed simultaneously with the mixing of the above epoxy compounds, or may be performed separately. Further, additives such as stabilizers such as pigments and weathering agents, fillers, and modifiers may be added simultaneously or separately during mixing.

In the present invention, by blending an epoxy compound and a heat stabilizer, an elastic body with excellent heat resistance and water resistance can be obtained.

Hereinafter, the present invention will be explained in more detail with reference to Examples. In the examples, reduced specific viscosity, tensile strength and elongation, and heat aging resistance were measured according to the following procedure. (1) Reduced specific viscosity Measured under the following conditions.

Solvent: Phenol/tetrachloroethane-6/4 (
Weight ratio) Concentration °50 / 25 - Temperature: 30 °C
A dumbbell-shaped No. 3 test piece is punched out, stretched at a speed of 50 mm per minute, and the load (Kp) at breakage is determined by the initial cross-sectional area (
The value divided by Ca) is defined as the strength (Kg/crl), and the ratio of the elongation of the sample until it breaks to the length of the original sample is defined as the elongation (%).

(3) Heat Aging Resistance The two-thickness flat plate sample obtained in (2) above was left in an oven at 150°C for a predetermined period of time, and then taken out and its tensile strength and elongation were measured according to the procedure in (2) above.

Production Example 1 70Kg of polytetramethylene terephthalate and 30Kf of ε-caprolactone were placed in a reaction vessel, and after barging, 2
After carrying out a melt reaction for 2 hours while stirring at 30°C, unreacted 1-caprolactone was removed under vacuum. The polyester block copolymer obtained had a reduced specific viscosity of 1.163. The tensile strength at break was 371 Kg/ctl, and the tensile elongation at break was 708%.

Production Example 2 1.5Kp of the polyester block copolymer chips obtained in Production Example 1 and 30.5Kp of phenyl glycidyl ether. C
1,) Riphenylphosphine 1.39 Pour into a radlum tumbler, stir at room temperature for 30 minutes,
The mixture was mixed and extruded at 230° C. using a twin-screw extruder, cooled with water, and then cut into chips. The reduced specific viscosity of the obtained chip was 1.044. Tensile strength at break is 354 Ky/ctll,
The tensile elongation at break was 680 inches.

Production Example 3 Polyester type block copolymer chips obtained in Production Example 1 1.5 KII and diethylene glycol diglycidyl ether 22. Of,) Riphenylphosphine 1
．． 3f was placed in a drum tumbler, and after stirring and mixing, chips were produced in the same manner as in Production Example 1.

The resulting chip had a reduced specific viscosity of 1.540, a tensile strength at break of 397.4/ca, and a tensile elongation at break of 478%.

Example 1 When preparing the polyester block copolymer assembly 7' of Production Example 2, tertiary butyl 4-
Chips were prepared by adding 4.5r of hydroxyphenyl)propione) E].

Example 2 17° Irganox 1010'' in Example 1
- Instead, chips were manufactured by adding "Lasmit" (dilauryl thiodigropionate) 4.5 F manufactured by Daiichi Kogyo Yakuhin Co., Ltd.

Example 3 Instead of “Irganox 1010” in Example 1, “Naragard 445” [4.4′-] manufactured by Uniroyal was used.
bis(α,α-dimethylbenzyl)diphenylamine)
Chips were manufactured by adding 4.5 f.

Example 4 When making the polyester type block copolymer composition chips of Production Example 3, the above-mentioned Irganox 1010"4.51 was added together with triphenylphosphine and diethylene glycol diglycidyl ether to produce chips.

Example 5 In place of "Irganox 1010" in Example 4, the aforementioned "Lasmit" 4,52 was added to produce chips.

Example 6 18 of “Irganox 1010” in Example 4
- Chips were manufactured by adding the above "Naragard 445" 4651 instead.

Comparative Example 1 Polyester block copolymer 1 obtained in Production Example 1
．． 5. Blend the above "Irganox 1010'4.5f" and mix in a drum tumbler, then heat at 230℃ for 40 minutes.
m+ (melted and extruded using a 12-screw extruder, cooled with water, and then cut into chips.

Margin Comparative Example 2 A chip was manufactured in the same manner as in Comparative Example 1 except that 4.5 g of 7 Naugard 445°' was added in place of "Irganox 1010" in Comparative Example 1.

The results of measuring the heat aging resistance of the chips obtained in Examples 1 to 6, Manufacturing Example 2.3, and Comparative Example 1.2 are shown in Tables 1 and 2 below.

The open storage time is 16th and 28th (150℃)
And so.

Table 1 Table 2 As is clear from Tables 1 and 2, the composition of the present invention was obtained when only the epoxy compound was blended (Production Example 2.3).
Or when only a heat stabilizer is blended (Comparative Example 1.2)
It exhibits significantly superior heat aging resistance compared to .

Patent applicant: Toyobo Co., Ltd. 21- =20-

Claims (2)

[Claims] (1) A polyester type block copolymer obtained by reacting a crystalline aromatic polyester and lactones with 1
A polyester block copolymer composition containing a functional or higher epoxy compound and a heat stabilizer. (2) Claim 1, characterized in that the heat stabilizer is one or more compounds selected from the group consisting of phenolic compounds, sulfur compounds, and diphenylamine compounds. The polyester type block copolymer composition described in 0